A detailed kinetic model for biogas steam reforming on Ni and catalyst deactivation due to sulfur poisoning

• Published in: Applied catalysis. A, General General, 2014-02, Vol.471, p.118-125
• Main Authors: Appari, Srinivas, Janardhanan, Vinod M., Bauri, Ranjit, Jayanti, Sreenivas, Deutschmann, Olaf
• Format: Article
• Language: English
• Subjects: Biogas; Catalysis; Catalyst poisoning; Catalysts; Chemistry; Deactivation; Exact sciences and technology; General and physical chemistry; Kinetics; Mathematical models; Modeling; Reactors; Reforming; Saturation; Sulfur; Surface chemistry; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0926-860X; 1873-3875
• DOI: 10.1016/j.apcata.2013.12.002

Comparison between the model predicted product composition during catalyst deactivation and experimental observations made at 973K for 20ppm H2S in the feed. •Detailed kinetic model for biogas reforming.•Kinetic model can predict catalyst deactivation in the presence of H2S.•1D fixed bed reactor modeling.•Comparison of model predictions with experimental data for biogas free from H2S.•Comparison of model predictions with experimental data for biogas containing 20–100ppm H2S. This paper deals with the development and validation of a detailed kinetic model for steam reforming of biogas with and without H2S. The model has 68 reactions among 8 gasphase species and 18 surface adsorbed species including the catalytic surface. The activation energies for various reactions are calculated based on unity bond index-quadratic exponential potential (UBI-QEP) method. The whole mechanism is made thermodynamically consistent by using a previously published algorithm. Sensitivity analysis is carried out to understand the influence of reaction parameters on surface coverage of sulfur. The parameters describing sticking and desorption reactions of H2S are the most sensitive ones for the formation of adsorbed sulfur. The mechanism is validated in the temperature range of 873–1200K for biogas free from H2S and 973–1173K for biogas containing 20–108ppm H2S. The model predicts that during the initial stages of poisoning sulfur coverages are high near the reactor inlet; however, as the reaction proceeds further sulfur coverages increase towards the reactor exit. In the absence of sulfur, CO and elemental hydrogen are the dominant surface adsorbed species. High temperature operation can significantly mitigate sulfur adsorption and hence the saturation sulfur coverages are lower compared to low temperature operation. Low temperature operation can lead to full deactivation of the catalyst. The model predicts saturation coverages that are comparable to experimental observation.