Non-catalytic partial oxidation of methane in biomass-derived syngas with high steam and hydrogen content optimal for subsequent synthesis process

Kertthong, Thiansiri; Schmid, Max; Scheffknecht, Günter

doi:10.1016/j.joei.2022.09.007

Cited by 8 publications

(1 citation statement)

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“…Furthermore, the rate of formation of CO in this reaction is unaffected by Ce-UiO-Cu in a nonaqueous solvent such as toluene (entries 21 and 22, Table S2, SI). We thus infer that thermal combustion of methane at 115 °C produces CO, 88 which then participates in the catalytic cycle of Ce-UiO-Cu(OH)-catalyzed methane conversion to CH 3 CO 2 H (eq S1, SI). The decrease of the rate of formation of CH 3 CO 2 H at a higher pressure of methane above 30 bar is presumably due to the diminishing rate of CO production at a higher CH 4 -to-O 2 ratio (Figure 4f).…”

Section: T H Imentioning

confidence: 99%

Selective Methane Oxidation to Acetic Acid Using Molecular Oxygen over a Mono-Copper Hydroxyl Catalyst

et al. 2023

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Acetic acid is an industrially important chemical, produced mainly via carbonylation of methanol using precious metal-based homogeneous catalysts. As a low-cost feedstock, methane is commercially transformed to acetic acid via a multistep process involving energy-intensive methane steam reforming, methanol synthesis, and, subsequently, methanol carbonylation. Here, we report a direct single-step conversion of methane to acetic acid using molecular oxygen (O 2 ) as the oxidant under mild conditions over a mono-copper hydroxyl site confined in a porous cerium metal−organic framework (MOF), Ce-UiO-Cu(OH). The Ce-UiO MOF-supported single-site copper hydroxyl catalyst gave exceptionally high acetic acid productivity of 335 mmolg cat −1 in 96% selectivity with a Cu TON up to 400 at 115 °C in water. Our spectroscopic and theoretical studies and controlled experiments reveal that the conversion of methane to acetic acid occurs via oxidative carbonylation, where methane is first activated at the copper hydroxyl site via σ-bond metathesis to afford Cu-methyl species, followed by carbonylation with in situ-generated carbon monoxide and subsequent hydrolysis by water. This work may guide the rational design of heterogeneous abundant metal catalysts for the activation and conversion of methane to acetic acid and other valuable chemicals under mild and environmentally friendly reaction conditions.

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Section: T H Imentioning

confidence: 99%