Pre-reforming of natural gas on a Ni catalyst Criteria for carbon free operation

Abstract Pre-reforming of natural gas has been studied on a nickel catalyst at 480–550 °C and 20 bar using a TEOM (Tapered Element Oscillating Microbalance) reactor. The focus has been on carbon formation and the main objective was to study the influence of C 2 –C 3 hydrocarbons in the methane feed on carbon deposition on the catalyst. Coking thresholds for different mixtures of hydrocarbons were determined by varying the steam to carbon (S/C) ratio at various temperatures. The steady-state coking rate decreases with increasing S/C ratio, and increases with increasing carbon number of the hydrocarbon. Unsaturated hydrocarbons show a strong effect on coking rates and on carbon thresholds. For mixtures of methane and propane/propene, the steady-state coking rate as well as the coking threshold decreased with a decrease in the mole fraction of propane/propene and with an increase in the hydrogen mole fraction. The coking rate revealed a complicated temperature dependency, and a minimum in the coking rate and in the coking threshold was detected at 500 °C. A relationship between the critical steam to carbon ratio and the thermodynamic carbon activity is also developed based on a suggested reaction mechanism, which can properly predict the role of hydrocarbon, hydrogen and water in carbon formation.

[1]  A. Datye,et al.  Sintering of Nickel Steam-Reforming Catalysts on MgAl2O4 Spinel Supports , 2001 .

[2]  J. Rostrup-Nielsen,et al.  Promotion of Steam Reforming Catalysts , 1998 .

[3]  Guy Marin,et al.  Eurokin. Chemical Reaction Kinetics in Practice , 2001 .

[4]  Kaoru Fujimoto,et al.  Development of highly stable nickel catalyst for methane-steam reaction under low steam to carbon ratio , 1996 .

[5]  David L. Trimm,et al.  Coke formation and minimisation during steam reforming reactions , 1997 .

[6]  Jens R. Rostrup-Nielsen,et al.  SULFUR-PASSIVATED NICKEL CATALYSTS FOR CARBON-FREE STEAM REFORMING OF METHANE , 1984 .

[7]  D. Trimm,et al.  The kinetics of gasification of carbon deposited on nickel catalysts , 1979 .

[8]  Gilbert F. Froment,et al.  Kinetic Study of the Carbon Filament Formation by Methane Cracking on a Nickel Catalyst , 1997 .

[9]  L. J. Christiansen,et al.  Activity of steam reforming catalysts: Role and assessment , 1988 .

[10]  J. Rostrup-Nielsen,et al.  Propane hydrogenolysis on sulfur- and copper-modified nickel catalysts , 2000 .

[11]  Thomas Sandahl Christensen,et al.  Adiabatic prereforming of hydrocarbons — an important step in syngas production , 1996 .

[12]  D. Lynch,et al.  Hydrogen control of carbon deposit morphology , 1995 .

[13]  D. Trimm Catalyst design for reduced coking (review) , 1983 .

[14]  De Chen,et al.  Catalyst deactivation studied by conventional and oscillating microbalance reactors , 1996 .

[15]  G. Froment,et al.  Filamentous carbon formation and gasification: Thermodynamics, driving force, nucleation, and steady-state growth , 1997 .

[16]  J. Rostrup-Nielsen,et al.  Carbon formation on nickel and nickel-copper alloy catalysts , 1998 .

[17]  J. Rostrup-Nielsen Equilibria of decomposition reactions of carbon monoxide and methane over nickel catalysts , 1972 .

[18]  De Chen,et al.  A study of coke formation kinetics by a conventional and an oscillating microbalance on steam reforming catalysts , 2000 .

[19]  Jens R. Rostrup-Nielsen,et al.  Steam reforming of liquid hydrocarbons , 1998 .

[20]  J. Rostrup-Nielsen Coking on nickel catalysts for steam reforming of hydrocarbons , 1974 .

[21]  David L. Trimm,et al.  The Formation and Removal of Coke from Nickel Catalyst , 1977 .

[22]  R. Stephens,et al.  The poisoning of a steam hydrocarbon gasification catalyst , 1972 .

[23]  J. Rostrup-Nielsen Mechanisms of carbon formation on nickel-containing catalysts , 1977 .