Effect of Catalytic Distribution on the Performance of Microreactor for Hydrogen Production through Methane Steam Reforming

Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands the development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH4/H2O gas mixtures react with Ni/CeO2(111) surfaces to form OH, CHx and CHxO at 300 K. All these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process accelerates. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3–0.7 eV for the complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation are rate-determining steps, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interaction between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results could pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.

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H2 production by methane steam reforming over Rh/Al2O3 catalyst packed in Cu foams: a strategy for the kinetic investigation in concentrated conditions

Catalysis Today ◽

10.1016/j.cattod.2021.06.003 ◽

2021 ◽

Author(s):

Matteo Ambrosetti ◽

Danilo Bonincontro ◽

Riccardo Balzarotti ◽

Alessandra Beretta ◽

Gianpiero Groppi ◽

...

Keyword(s):

Steam Reforming ◽

H2 Production ◽

Methane Steam Reforming ◽

Kinetic Investigation ◽

Methane Steam ◽

Al2o3 Catalyst

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Reaction Pathway for Coke-Free Methane Steam Reforming on a Ni/CeO2 Catalyst: Active Sites and Role of Metal-Support Interactions

10.26434/chemrxiv.14686740 ◽

2021 ◽

Author(s):

Agustin Salcedo ◽

Pablo Lustemberg ◽

Ning Rui ◽

Robert M. Palomino ◽

Zongyuan Liu ◽

...

Keyword(s):

High Activity ◽

Steam Reforming ◽

Active Sites ◽

Density Functional ◽

Ambient Pressure ◽

Carbon Accumulation ◽

Methane Steam Reforming ◽

Severe Problem ◽

Methane Steam ◽

Water Activation

Methane steam reforming (MSR) plays a key role in the production of syngas and hydrogen from natural gas. The increasing interest in the use of hydrogen for fuel cell applications demands the development of catalysts with high activity at reduced operating temperatures. Ni-based catalysts are promising systems because of their high activity and low cost, but coke formation generally poses a severe problem. Studies of ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) indicate that CH4/H2O gas mixtures react with Ni/CeO2(111) surfaces to form OH, CHx and CHxO at 300 K. All these species are easy to form and desorb at temperatures below 700 K when the rate of the MSR process accelerates. Density functional theory (DFT) modeling of the reaction over ceria-supported small Ni nanoparticles predicts relatively low activation barriers between 0.3–0.7 eV for the complete dehydrogenation of methane to carbon and the barrierless activation of water at interfacial Ni sites. Hydroxyls resulting from water activation allow CO formation via a COH intermediate with a barrier of about 0.9 eV, which is much lower than that through a pathway involving lattice oxygen from ceria. Neither methane nor water activation are rate-determining steps, and the OH-assisted CO formation through the COH intermediate constitutes a low-barrier pathway that prevents carbon accumulation. The interaction between Ni and the ceria support and the low metal loading are crucial for the reaction to proceed in a coke-free and efficient way. These results could pave the way for further advances in the design of stable and highly active Ni-based catalysts for hydrogen production.

Download Full-text