Kinetic Modeling for the Combined Pyrolysis and Steam Gasification of Petroleum Coke and Experimental Determination of the Rate Constants by Dynamic Thermogravimetry in the 500−1520 K Range

The detailed kinetic mechanisms for the combined endothermic pyrolysis and steam gasification of petroleum coke are formulated using elementary chemisorption and reaction steps. The pyrolysis model is based on a linear combination of first-order decomposition rates of pseudo components. The gasification model is based on the oxygen-exchange mechanism describing reversible O-transfer surface reactions followed by a unidirectional gasification step, and on an extended mechanism describing, in addition, reversible steam sorption as OH/H groups and irreversible surface chemistry. The kinetic rate laws of Langmuir−Hinshelwood type are derived by assuming sorption equilibrium and by considering inhibition due to recombination of adsorbed oxygen and competition for active sites. The Arrhenius parameters of the rate constants for the pyrolysis and gasification of Flexicoke and Petrozuata Delayed coke are experimentally determined by dynamic thermogravimetric analyses with Ar, H2O, CO2, and H2O−CO2 mixtures in the...

[1]  S. Porada The reactions of formation of selected gas products during coal pyrolysis , 2004 .

[2]  M. Romero,et al.  Hydrogen production by steam-gasification of petroleum coke using concentrated solar power—I. Thermodynamic and kinetic analyses , 2005 .

[3]  E. Mészáros,et al.  Thermogravimetric and Reaction Kinetic Analysis of Biomass Samples from an Energy Plantation , 2004 .

[4]  Arnold E. Reif,et al.  The Mechanism of the Carbon Dioxide–Carbon Reaction , 1952 .

[5]  A. Gómez-Barea,et al.  Reaction-diffusion model of TGA gasification experiments for estimating diffusional effects , 2005 .

[6]  J. Gadsby,et al.  The mechanism of the carbon dioxide-carbon reaction , 1948, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[7]  J. Gadsby,et al.  The kinetics of the reactions of the steam-carbon system , 1946, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[8]  S. Kiil,et al.  Use of spray dry absorption product in wet flue gas desulphurisation plants: pilot-scale experiments , 2002 .

[9]  S. Porada,et al.  Formation of C1C3 hydrocarbons during pressure pyrolysis and hydrogasification in relation to structural changes in coal , 1995 .

[10]  A. Steinfeld,et al.  Kinetic investigation on steam gasification of charcoal under direct high-flux irradiation , 2003 .

[11]  A. Gordon,et al.  Distribution of activation energy model applied to the rapid pyrolysis of coal blends , 2004 .

[12]  K. Heek,et al.  Kinetic studies of steam gasification of char in the presence of H2, CO2 and CO , 1985 .

[13]  S. Walas Reaction kinetics for chemical engineers , 1959 .

[14]  Jd Blackwood,et al.  The Reaction of Carbon with Carbon Dioxide at High Pressure , 1960 .

[15]  D. Kocaefe,et al.  Green coke pyrolysis: investigation of simultaneous changes in gas and solid phases , 1995 .

[16]  Jd Blackwood,et al.  The carbon-steam reaction at high pressure , 1958 .

[17]  Sabri Ergun,et al.  Kinetics of the Reactions of Carbon Dioxide and Steam with Coke , 1962 .

[18]  K. W. Sykes,et al.  The mechanism of the steam-carbon reaction , 1948, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.