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Theses Doctoral

Developing an energy efficient steam reforming process to produce hydrogen from sulfur-containing fuels

Simson, Amanda Elizabeth

Hydrogen powered fuel cells have the potential to produce electricity with higher efficiency and lower emissions than conventional combustion technology. In order to realize the benefits of a hydrogen fuel cell an efficient method to produce hydrogen is needed. Currently, over 90% of hydrogen is produced from the steam reforming of natural gas. However, for many applications including fuel cell vehicles, the use of a liquid fuel rather than natural gas is desirable. This work investigates the feasibility of producing hydrogen efficiently by steam reforming E85 (85% ethanol/15% gasoline), a commercially available sulfur-containing transportation fuel. A Rh-Pt/SiO2-ZrO2 catalyst has demonstrated good activity for the E85 steam reforming reaction. An industrial steam reforming process is often run less efficiently, with more water and at higher temperatures, in order to prevent catalyst deactivation. Therefore, it is desirable to develop a process that can operate without catalyst deactivation at more energy efficient conditions. In this study, the steam reforming of a sulfur-containing fuel (E85) was studied at near stoichiometric steam/carbon ratios and at 650C, conditions at which catalyst deactivation is normally measured. At these conditions the catalyst was found to be stable steam reforming a sulfur-free E85. However, the addition of low concentrations of sulfur significantly deactivated the catalyst. The presence of sulfur in the fuel caused catalyst deactivation by promoting ethylene which generates surface carbon species (coke) that mask catalytic sites. The amount of coke increased during time on stream and became increasingly graphitic. However, the deactivation due to both sulfur adsorption and coke formation was reversible with air treatment at 650C. However, regenerations were found to reduce the catalyst life. Air regenerations produce exotherms on the catalyst surface that cause structural changes to the catalyst. During regenerations the accessibility of the precious metal particles is reduced which causes the catalyst to deactivate more rapidly during subsequent steam reforming cycles. Changes to the carrier morphology also occur at these conditions. Regenerating the catalyst before significant deactivation is measured can improve the stability of the catalyst. Thus a process with preemptive controlled air regenerations is proposed in order to run a steam reforming process with sulfur containing fuels.

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More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
Castaldi, Marco J.
Degree
Ph.D., Columbia University
Published Here
May 14, 2013
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