Selective Oxidation of Methane with Hydrogen Peroxide Towards Formic Acid in a Micro Fixed‐Bed Reactor

Zuo, Hualiang; Meynen, Vera; Klemm, Elias

doi:10.1002/cite.201600174

Cited by 5 publications

(2 citation statements)

References 29 publications

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“…A shift in selectivity toward ethene from acetic acid has been observed when adding Cu into the catalyst. Klemm and colleagues , studied methane oxidation using microchannel reactors. Due to a very low liquid-to-solid ratio, formic acid was found to be the main product even when a Cu-Fe-Silicalite-1 catalyst was used.…”

Section: Liquid Phase Selective Methane Oxidationmentioning

confidence: 99%

Methane Oxidation to Methanol

et al. 2022

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The direct transformation of methane to methanol remains a significant challenge for operation at a larger scale. Central to this challenge is the low reactivity of methane at conditions that can facilitate product recovery. This review discusses the issue through examination of several promising routes to methanol and an evaluation of performance targets that are required to develop the process at scale. We explore the methods currently used, the emergence of active heterogeneous catalysts and their design and reaction mechanisms and provide a critical perspective on future operation. Initial experiments are discussed where identification of gas phase radical chemistry limited further development by this approach. Subsequently, a new class of catalytic materials based on natural systems such as iron or copper containing zeolites were explored at milder conditions. The key issues of these technologies are low methane conversion and often significant overoxidation of products. Despite this, interest remains high in this reaction and the wider appeal of an effective route to key products from C–H activation, particularly with the need to transition to net carbon zero with new routes from renewable methane sources is exciting.

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Section: Liquid Phase Selective Methane Oxidationmentioning

confidence: 99%

Methane Oxidation to Methanol

et al. 2022

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“…Subsequent studies used H 2 and O 2 to form H 2 O 2 in situ, which also produced CH 3 OH selectively through the formation of a high flux of OH radicals . Catalytic materials other than AuPd can activate H 2 O 2 for selective CH 4 conversion, with Fe-ZSM-5 producing 93.5% selectivity to CH 3 OH at 50 °C, vanadate complexes for HCO 2 CH 3 formation with 71% selectivity at 80 °C, and the formation of formic acid on Cu–Fe-silicalite 1 with 96.7% selectivity at 100 °C . H 2 O 2 can also selectively oxidize CH 4 to CH 3 OH in a plasma setting, where the formation of OH radicals is key to the formation of CH 3 OH .…”

Section: Introductionmentioning

confidence: 99%

Direct Injection of Hydrogen Peroxide for Selective Homogeneous Conversion of Methane into Higher Hydrocarbons

Yoshida,

Movick,

Obata

et al. 2024

Ind. Eng. Chem. Res.

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The impact of direct H 2 O 2 injection on the selective CH 4 coupling reaction at high temperatures was investigated both experimentally and by kinetic modeling to provide insight into the reaction mechanism of the catalytic oxidative coupling of methane (OCM). H 2 O 2 injection transforms CH 4 into C 2 H 6 and C 2 H 4 at high selectivity, confirming the effectiveness of the involvement of H 2 O 2 by generating OH radicals in OCM. For carbon oxides, there was only CO formation without CO 2 at CH 4 conversions at or below 10%, as expected from the pure contribution of the gas phase. These results were consistent with simulation results using kinetic modeling of gas-phase elementary reactions. Rate of production (ROP) analysis suggests that OH radicals formed from H 2 O 2 decomposition were responsible for the high selectivity toward C 2 products. The major loss of C 2 selectivity and CH 4 conversion is due to HO 2 radicals, a secondary product in H 2 O 2 decomposition. The HO 2 radicals were found to both oxidize CH 3 radicals and neutralize OH radicals. The kinetic model consistently overpredicted the CH 4 conversion and C 2 selectivity over the experimental results, which can be attributed to the radical quenching and overoxidation reaction on the surface of the quartz tube reactor. The findings in this work help create a better understanding of the requirements of selective C 2 formation under OCM conditions.

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