Hydrogen Production for PEM Fuel Cells via Oxidative Steam Reforming of Methanol Using Cu-Al Catalysts Modified With Ce and Cr

Abstract

The performance of Cu-Ce-Al-oxide and Cu-Cr-Al-oxide catalysts of varying compositions prepared by co-precipitation method was evaluated for the PEM fuel cell grade hydrogen production via oxidative steam reforming of methanol (OSRM). The limitations of partial oxidation and steam reforming of methanol for the hydrogen production for PEM fuel cell could be overcome using OSRM and can be performed auto-thermally with idealized reaction stoichiomatry. Catalysts surface area and pore volume were determined using N2 adsorption-desorption method. The final elemental compositions were determined using atomic absorption spectroscopy. Crystalline phases of catalyst samples were determined by X-ray diffraction (XRD) technique. Temperature programmed reduction (TPR) demonstrated that the incorporation of Ce improved the copper reducibility significantly compared to Cr promoter. The OSRM was carried out in a fixed bed catalytic reactor. Reaction temperature, contact-time (W/F) and oxygen to methanol (O/M) molar ratio varied from 200–300°C, 3–21 kgcat s mol−1 and 0–0.5 respectively. The steam to methanol (S/M) molar ratio = 1.4 and pressure = 1 atm were kept constant. Catalyst Cu-Ce-Al:30-10-60 exhibited 100% methanol conversion and 152 mmol s−1 kgcat−1 hydrogen production rate at 300°C with carbon monoxide formation as low as 1300 ppm, which reduces the load on preferential oxidation of CO to CO2 (PROX) significantly before feeding the hydrogen rich stream to the PEM fuel cell as a feed. The higher catalytic performance of Ce containing catalysts was attributed to the improved Cu reducibility, higher surface area, and better copper dispersion. Reaction parameters were optimized in order to maximize the hydrogen production and to keep the CO formation as low as possible. The time-on-stream stability test showed that the Cu-Ce-Al-oxide catalysts subjected to a moderate deactivation compared to Cu-Cr-Al-oxide catalysts. The amount of carbon deposited onto the catalysts was determined using TG/DTA thermogravimetric analyzer. C1s spectra were obtained by surface analysis of post reaction catalysts using X-ray photoelectron spectroscopy (XPS) to investigate the nature of coke deposited.