Journal of Catalysis 238 (2006) 309–320 www.elsevier.com/locate/jcat Low-temperature steam reforming of jet fuel in the absence and presence of sulfur over Rh and Rh–Ni catalysts for fuel cells James J. Strohm, Jian Zheng, Chunshan Song ∗ Clean Fuels and Catalysis Program, The Energy Institute, and Department of Energy & Geo-Environmental Engineering, The Pennsylvania State University, 209 Academic Projects Building, University Park, PA 16802, USA Received 5 September 2005; revised 28 November 2005; accepted 5 December 2005 Available online 20 January 2006 Abstract This work is a comparative study on low-temperature steam reforming of jet fuel over Rh and Rh–Ni loaded on CeO 2 -modified Al 2 O 3 support in the absence and presence of different amounts of organic sulfur. Rh loaded on CeO 2 –Al 2 O 3 support can promote reforming of sulfur-free or desulfurized jet fuel at <520 ◦ C with >97% conversion to syngas and CH 4 . However, monometallic Rh/CeO 2 –Al 2 O 3 catalyst deactivates by S poisoning. During the reforming of liquid fuel with >10 ppmw S, catalytic activity rapidly decreases when the amount of sulfur in the fuel flown over the catalyst reaches the level corresponding to a S fuel :Rh surf atomic ratio of 0.28–0.30 (for which the amount of surface Rh is based on H 2 and CO pulse chemisorption analysis). Methane formation is even more sensitive (than conversion) to sulfur poisoning. At a S fuel :Rh surf ratio of 0.15, methane selectivity over the Rh/CeO 2 –Al 2 O 3 catalyst begins to decline. Addition of Ni by co-impregnation into the Rh/CeO 2 –Al 2 O 3 catalyst leads to much higher sulfur tolerance. Ni acts as a protective and sacrificial metal for Rh in the Rh–Ni/CeO 2 –Al 2 O 3 catalyst. Ni surface saturation of sulfur was found to occur at a S fuel :Ni surf ratio of 0.59–0.60, corresponding to a S fuel :Rh surf ratio of 1.1 for 2% Rh–10% Ni/CeO 2 –Al 2 O 3 . The bimetallic Rh–Ni/CeO 2 –Al 2 O 3 catalyst allows for successful low-temperature reforming of a JP-8 jet fuel containing 22 ppm sulfur for 72 h with >95% conversion. TPR and XPS analysis reveals close Rh–Ni metal–metal interactions. The presence of Ni increases the temperature for Rh reduction in TPR, whereas Rh helps maintain Ni in a reduced state in an oxidative atmosphere.  2005 Elsevier Inc. All rights reserved. Keywords: Catalyst; Rh; Rh–Ni; Bimetallic; Steam reforming; Jet fuel; Sulfur tolerance 1. Introduction Fuel processing has become an important subject in catal- ysis research for fuel cells [1–4]. The demand for on-site and on-board syngas and hydrogen production is increasing with growing interest in hydrogen energy and fuel cells for the sup- ply of cleaner and more efficient electric power supply [1–4]. Steam reforming of logistic fuels, such as jet fuel and diesel fuel, is a viable and effective means of syngas and hydrogen production for solid-oxide fuel cell and proton-exchange mem- brane fuel cell, respectively, due to the existing infrastructure and high energy density of these fuels. Along with the advan- tages of using liquid hydrocarbons for portable and stationary * Corresponding author. Fax: +1 814 865 3248. E-mail address: csong@psu.edu (C. Song). fuel processors are some major challenges, as discussed in a recent review [3]. Industrial hydrogen production is generally conducted by steam reforming of natural gas over supported nickel catalysts [5–7]. Numerous studies have been conducted on strategies for processing conditions and catalyst formulations to minimize carbon formation during steam reforming [8–12]. However, the use of higher hydrocarbons that contain aromatics can pose a threat of carbon formation during steam reforming both on the catalyst and before the catalyst bed [13]. One approach to min- imizing carbon formation on the catalyst is by using noble met- als, such as Ru and Rh, which do not produce carbon filaments due to poor carbon solubility in the metal [13]. Another ap- proach is to first perform low-temperature steam reforming (or prereforming) to reform the higher hydrocarbons to methane, hydrogen, and carbon oxides, followed by high-temperature reforming of the reformate into hydrogen and carbon oxides. 0021-9517/$ – see front matter  2005 Elsevier Inc. All rights reserved. doi:10.1016/j.jcat.2005.12.010