Operating strategies for fuel processing systems with a focus on water–gas shift reactor stability

This contribution deals with the development of suitable operating strategies for diesel/kerosene-fueled fuel cell APUs. The focus is on the autothermal reformer (ATR) and the water–gas shift (WGS) reactor. In the first part shutdown experiments under high-temperature shift (HTS) conditions were used to identify the possible detrimental effect of higher hydrocarbons on the activity and stability of two commercial WGS catalysts. The results indicated that 220ppmv higher hydrocarbons had no negative effect on the catalyst activity/stability. The second part presents fuel processing system experiments, which revealed much higher concentrations of higher hydrocarbons during transients like startup/shutdown than the concentrations investigated in the first part. Through the development of new startup/shutdown strategies concentrations of higher hydrocarbons were lowered by a factor of up to 10 for startup and of up to 400 for shutdown. The results were reproduced using four different diesel and kerosene fuels. The newly developed strategies improve fuel conversion in the reformer and may possibly prevent catalyst deactivation in the water–gas shift reactor during transient conditions.

[1]  G. Ertl,et al.  Handbook of Heterogeneous Catalysis , 1997 .

[2]  Lars J. Pettersson,et al.  Autothermal reforming of Fischer–Tropsch diesel over alumina and ceria–zirconia supported catalysts , 2013 .

[3]  Werner Lehnert,et al.  Operational Experience from a 5 kWe HT-PEFC System with Reforming of Diesel and Kerosene , 2013 .

[4]  Polycarpos Falaras,et al.  Low-temperature water-gas shift reaction over Au/CeO2 catalysts , 2002 .

[5]  R. C. Samsun,et al.  Fuel Processing of Diesel and Kerosene for Auxiliary Power Unit Applications , 2013 .

[6]  Zhen Ma,et al.  Water-gas shift on gold catalysts: catalyst systems and fundamental studies. , 2013, Physical chemistry chemical physics : PCCP.

[7]  Bin Wang,et al.  A comparative study of the deactivation mechanisms of the Au/CeO2 catalyst for water–gas shift under steady-state and shutdown/start-up conditions in realistic reformate , 2013 .

[8]  Angeliki A. Lemonidou,et al.  Methane steam reforming at low temperature: Effect of light alkanes’ presence on coke formation , 2015 .

[9]  Maria Flytzani-Stephanopoulos,et al.  On the issue of the deactivation of Au-ceria and Pt-ceria water-gas shift catalysts in practical fuel-cell applications. , 2006, Angewandte Chemie.

[10]  Siew Hwa Chan,et al.  Transient carbon monoxide poisoning kinetics during warm-up period of a high-temperature PEMFC – Physical model and parametric study , 2015 .

[11]  A. Ersöz,et al.  Design studies for monolithic high temperature shift catalysts: Effect of operational parameters , 2013 .

[12]  Zaiku Xie,et al.  Robust Au/Ce0.4Zr0.6O2 Catalyst for Dynamic Shutdown/Startup of the Water–Gas Shift Reaction in Realistic Reformate with <1 % O2 , 2014 .

[13]  Robert J. Farrauto,et al.  Ceria-based palladium zinc catalysts as promising materials for water gas shift reaction , 2014 .

[14]  Bongjin Simon Mun,et al.  Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction , 2007 .

[15]  Raymond J. Gorte,et al.  Deactivation Mechanisms for Pd/Ceria During the Water-Gas Shift Reaction , 2002 .

[16]  Detlef Stolten,et al.  Investigation of Operating Parameters in Conjunction with Catalyst Deactivation of the Water-Gas Shift Reactor in a Fuel Cell System , 2015 .

[17]  Maria Flytzani-Stephanopoulos,et al.  Reaction-Relevant Gold Structures in the Low Temperature Water-Gas Shift Reaction on Au-CeO2 , 2008 .

[18]  Wenjie Shen,et al.  Stabilized gold nanoparticles on ceria nanorods by strong interfacial anchoring. , 2012, Journal of the American Chemical Society.

[19]  Levi T. Thompson,et al.  Deactivation of Au/CeOx water gas shift catalysts , 2005 .

[20]  J. M. Zalc,et al.  Are Noble Metal-Based Water–Gas Shift Catalysts Practical for Automotive Fuel Processing? , 2002 .

[21]  Helen Daly,et al.  The effect of reaction conditions on the stability of Au/CeZrO4 catalysts in the low-temperature water–gas shift reaction , 2010 .

[22]  R. C. Samsun,et al.  Start‐Up of HT‐PEFC Systems Operating with Diesel and Kerosene for APU Applications , 2014 .

[23]  Werner Lehnert,et al.  HT-PEFC Systems Operating with Diesel and Kerosene for APU Application , 2012 .

[24]  Werner Lehnert,et al.  Design and test of a 5kWe high-temperature polymer electrolyte fuel cell system operated with diesel and kerosene , 2014 .

[25]  Giancarlo Baldi,et al.  Effects of tar model compounds on commercial water gas shift catalysts , 2012 .

[26]  Robert J. Farrauto,et al.  Mechanism of aging for a Pt/CeO2-ZrO2 water gas shift catalyst , 2006 .

[27]  Rolf Jürgen Behm,et al.  Influence of CO2 and H2 on the low-temperature water–gas shift reaction on Au/CeO2 catalysts in idealized and realistic reformate , 2007 .

[28]  Detlef Stolten,et al.  Long-term stability at fuel processing of diesel and kerosene , 2014 .

[29]  Jens R. Rostrup-Nielsen,et al.  Concepts in Syngas Manufacture , 2011 .

[30]  Yung-Hsiang Cheng,et al.  Urban transportation energy and carbon dioxide emission reduction strategies☆ , 2015, Applied Energy.

[31]  Z. Pors.  Eduktvorbereitung und Gemischbildung in Reaktionsapparaten zur autothermen Reformierung von dieselähnlichen Kraftstoffen , 2006 .

[32]  Raymond J. Gorte,et al.  A comparative study of water-gas-shift reaction over ceria supported metallic catalysts , 2001 .

[33]  Robert J. Farrauto,et al.  Deactivation of Pt/CeO2 water-gas shift catalysts due to shutdown/startup modes for fuel cell applications , 2005 .

[34]  Erdogan Gulari,et al.  Comparative studies of low-temperature water-gas shift reaction over Pt/CeO2, Au/CeO2, and Au/Fe2O3 catalysts , 2003 .

[35]  R. J. Behm,et al.  Influence of H2, CO2 and H2O on the activity and deactivation behavior of Au/CeO2 catalysts in the water gas shift reaction at 300 °C , 2010 .

[36]  Ye Li,et al.  An empirical study on the influencing factors of transportation carbon efficiency: Evidences from fifteen countries , 2015 .

[37]  Semant Jain,et al.  Techno-economic analysis of fuel cell auxiliary power units as alternative to idling , 2006 .

[38]  Christiane Wiethege.  Mobile Brenngaserzeugungssysteme mit Mitteldestillaten für Hochtemperatur-PEFC , 2013 .

[39]  A. Ghenciu,et al.  Review of fuel processing catalysts for hydrogen production in PEM fuel cell systems , 2002 .

[40]  R. Behm,et al.  Influence of the catalyst surface area on the activity and stability of Au/CeO2 catalysts for the low-temperature water gas shift reaction , 2007 .

[41]  Detlef Stolten,et al.  A novel reactor type for autothermal reforming of diesel fuel and kerosene , 2015 .

[42]  Lars J. Pettersson,et al.  Autothermal reforming of low-sulfur diesel over bimetallic RhPt supported on Al2O3, CeO2–ZrO2, SiO2 and TiO2 , 2011 .

[43]  Detlef Stolten,et al.  Fuel cell systems with reforming of petroleum-based and synthetic-based diesel and kerosene fuels for APU applications , 2015 .

[44]  R. J. Behm,et al.  Activity, stability and deactivation behavior of Au/CeO2 catalysts in the water gas shift reaction at increased reaction temperature (300 °C) , 2009 .

[45]  Raymond J. Gorte,et al.  Studies of the water-gas-shift reaction on ceria-supported Pt, Pd, and Rh: Implications for oxygen-storage properties , 1998 .

[46]  Ute Kaiser,et al.  Deactivation of a Au/CeO2 catalyst during the low-temperature water-gas shift reaction and its reactivation : A combined TEM, XRD, XPS, DRIFTS, and activity study , 2007 .

[47]  Janko Petrovčič,et al.  A model-based approach to battery selection for truck onboard fuel cell-based APU in an anti-idling application , 2015 .

[48]  Maria Flytzani-Stephanopoulos,et al.  Activity and stability of low-content gold–cerium oxide catalysts for the water–gas shift reaction , 2005 .