Chemical Engineering Science 62 (2007) 5436 – 5443 www.elsevier.com/locate/ces Selective production of hydrogen via oxidative steam reforming of methanol using Cu–Zn–Ce–Al oxide catalysts Sanjay Patel a , b , K.K. Pant a , ∗ a Department of Chemical Engineering, Indian Institute of Technology, Hauz Khas, New Delhi 110016, India b Department of Chemical Engineering, Institute of Technology, Nirma University of Science and Technology, Ahmedabad 382481, India Received 15 June 2006; received in revised form 19 January 2007; accepted 29 January 2007 Available online 15 February 2007 Abstract The oxidative steam reforming of methanol (OSRM) was carried out to produce the hydrogen selectively for polymer electrolyte membrane (PEM) fuel cell applications over Cu–Zn–Ce–Al oxide and Cu–Zn–Al oxide catalysts of varying compositions prepared by co-precipitation method. Catalyst performance was evaluated in a packed bed reactor over a wide range of operating conditions, and reaction parameters were optimized in order to maximize the hydrogen production with minimum carbon monoxide formation. The incorporation of ceria in Cu–Zn–Al oxide catalysts enhanced the activity greatly compared to without it. The Cu/Zn/Ce/Al:30/20/10/40 exhibited 100% methanol conversion and 244 mmol s -1 kg -1 cat hydrogen rate at 553 K with carbon monoxide as low as 995 ppm, which reduces the load on preferential oxidation of CO to CO 2 significantly before feeding the hydrogen rich stream to the PEM fuel cell as a feed. Ceria had improved the dispersion and specific surface area of copper in multi-component Cu–Zn–Ce–Al oxide catalysts which were confirmed by the physicochemical properties, X-ray diffraction (XRD), temperature programmed reduction (TPR) and CO chemisorption studies. The chemisorption studies were performed at 193 K in order to hinder the spillover of carbon monoxide to ceria. The time-on-stream stability test had shown Cu–Zn–Ce–Al oxide catalysts as more stable compared to Cu–Zn–Al oxide catalysts. The amount of carbon deposited onto the catalysts was determined using TG/DTA thermogravimetric analyzer and the type of carbon species were identified using C1s X-ray photoelectron spectroscopy (XPS) spectra.  2007 Elsevier Ltd. All rights reserved. Keywords: Hydrogen; OSRM; Ceria; PEM fuel cell 1. Introduction Hydrogen is expected to play a major role in the future as a carbon free energy carrier. Its use in the vehicles via poly- mer electrolyte membrane (PEM) fuel cells can offer the non- toxic tail-pipe emissions and high over all efficiency compared to conventional internal combustion engines (Edwards et al., 1998; Bowers et al., 2006). The on-board storage of hydro- gen with high energy density is facing some technical prob- lems (Breen and Ross, 1999; Raimondi et al., 2002). One promising solution to this can be an on-board production of hydrogen using liquid hydrocarbons like methanol (Patel and Pant, 2006c; Yan et al., 2006), ethanol (Sahoo et al., 2007), ∗ Corresponding author. Tel.: +91 11 26596172; fax: +91 11 26581120. E-mail address: kkpant@chemical.iitd.ac.in (K.K. Pant). 0009-2509/$ - see front matter  2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.ces.2007.01.066 dimethyl ether (Semelsberger et al., 2006), etc. Methanol offers several advantages for the hydrogen production compared to other liquid organics (Velu et al., 2001; Patel and Pant, 2006a). There are different routs available for the hydrogen production from methanol as follows. One is partial oxidation of methanol (POM), CH 3 OH + 0.5O 2 ←→ 2H 2 + CO 2 , H 0 =-192 kJ mol -1 . (1) This is a highly exothermic reaction which leads to the problem of heat removal and reactor temperature control, and also pro- duces significant amount of CO (Wang et al., 2003). Another route is the steam reforming of methanol (SRM), CH 3 OH + H 2 O ←→ 3H 2 + CO 2 , H 0 = 49.5 kJ mol -1 . (2)