Probing the methanol-assisted autocatalytic formation of methanol over Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> by high-pressure methanol and methyl formate pulses

Schwiderowski, Philipp; Stürmer, Sascha

doi:10.1039/d2re00185c

Cited by 3 publications

(9 citation statements)

References 38 publications

(69 reference statements)

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“…A further study of Muhler and co‐workers also supported the autocatalytic effect of co‐fed CH 3 OH [26] . In this study, CH 3 OH was, however, not continuously co‐fed but periodically pulsed.…”

Section: Co2 Hydrogenation To Ch3oh Over Cu‐based Catalystssupporting

confidence: 68%

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

Zhao,

Han,

Kondratenko

2023

ChemCatChem

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Carbon dioxide (CO2) hydrogenation to methanol (CH3OH) is one of the most promising approaches to provide this platform chemical and to close carbon cycles. In this minireview, we systematically analyze primary and secondary reactions which can take place in this reaction over Cu‐based catalysts. In addition to repeatedly discussed reverse water gas shift reaction (RWGS) and CH3OH production directly from CO2, we consider decomposition, dehydration, dehydrogenation, and steam reforming of the desired alcohol. These reactions are usually ignored in the studies dealing with CO2 hydrogenation to CH3OH but can worsen the catalyst efficiency. Apart from the corresponding thermodynamic analysis, proposed reaction mechanisms and active sites are described and discussed. The effects of co‐fed water, CH3OH and methyl formate on catalyst performance are critically scrutinized, too. We also provide several criteria for unambiguous comparison of different catalysts in terms of CH3OH selectivity and their activity.

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Section: Co2 Hydrogenation To Ch3oh Over Cu‐based Catalystssupporting

confidence: 68%

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

Zhao,

Han,

Kondratenko

2023

ChemCatChem

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“…519 Muhler et al picked up on these observations and used their high-pressure pulse apparatus 461 (section 8.2) to pulse methanol and methyl formate at high pressures into a working catalytic CO/CO 2 /H 2 hydrogenation process. 399 Through quantification of these pulsing experiments, made over a range of methanol concentrations (Figure 88a), they confirmed that the dosing of methanol itself results in an overproduction of methanol by the catalyst. When dosing methyl formate, it would be expected that double the amount of methanol would be detected at the reactor outlet, due to the decomposition of methyl formate into two methanol molecules.…”

Section: Autocatalysis Induced By Methanolmentioning

confidence: 71%

“…Therefore, the methanol produced during the reaction could be a potential promoter that could lead to a further autocatalytic synthetic mechanism. This idea was only subsequently picked up on almost 20 years later. , …”

Section: –2009mentioning

confidence: 99%

“…The mole fractions of methanol pulsed into the gas feed are indicated above the pulses and the respective gas flow rates on the bottom. (b) The proposed methanol-assisted autocatalytic cycle for high pressure-methanol synthesis over Cu/ZnO/Al 2 O 3 catalysts including the methyl formate ester as intermediate according to Shi et al and Thrane et al Adapted with permission from ref . Copyright 2022 Royal Chemical Society.…”

Section: –2022mentioning

confidence: 99%

“…The methylformate can then be further hydrogenated to release one methanol and a formaldehyde, which is then hydrogenated to methoxy and finally to a second methanol molecule. This path has a significant positive influence on the overall performance of the catalyst , and leads to significant rate enhancements (reported up to a 2-fold rate increase) at methanol concentrations of around 1%. Therefore, this effect will occur in most areas of the methanol reactor.…”

Section: Potential Active Sites and Reaction Mechanisms Over Czamentioning

confidence: 99%

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The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

Beck,

Newton,

van de Water

et al. 2024

Chem. Rev.

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The activity and durability of the Cu/ZnO/Al 2 O 3 (CZA) catalyst formulation for methanol synthesis from CO/CO 2 /H 2 feeds far exceed the sum of its individual components. As such, this ternary catalytic system is a prime example of synergy in catalysis, one that has been employed for the large scale commercial production of methanol since its inception in the mid 1960s with precious little alteration to its original formulation. Methanol is a key building block of the chemical industry. It is also an attractive energy storage molecule, which can also be produced from CO 2 and H 2 alone, making efficient use of sequestered CO 2 . As such, this somewhat unusual catalyst formulation has an enormous role to play in the modern chemical industry and the world of global economics, to which the correspondingly voluminous and ongoing research, which began in the 1920s, attests. Yet, despite this commercial success, and while research aimed at understanding how this formulation functions has continued throughout the decades, a comprehensive and universally agreed upon understanding of how this material achieves what it does has yet to be realized. After nigh on a century of research into CZA catalysts, the purpose of this Review is to appraise what has been achieved to date, and to show how, and how far, the field has evolved. To do so, this Review evaluates the research regarding this catalyst formulation in a chronological order and critically assesses the validity and novelty of various hypotheses and claims that have been made over the years. Ultimately, the Review attempts to derive a holistic summary of what the current body of literature tells us about the fundamental sources of the synergies at work within the CZA catalyst and, from this, suggest ways in which the field may yet be further advanced.

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Effect of hydrothermal environment on Cu-ZnO/Al2O3 catalyst for hydrogenation of CO2 to methanol

Li,

Guo,

Zhao

et al. 2023

Molecular Catalysis

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Probing the methanol-assisted autocatalytic formation of methanol over Cu/ZnO/Al₂O₃ by high-pressure methanol and methyl formate pulses

Abstract: Using high-pressure methanol and methyl formate pulses as a surface-sensitive operando method for high-pressure methanol synthesis over Cu/ZnO/Al2O3, the recently found autocatalytic pathway was confirmed. The autocatalytic effect is assumed...

Cited by 3 publications

References 38 publications

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts

Effect of hydrothermal environment on Cu-ZnO/Al2O3 catalyst for hydrogenation of CO2 to methanol

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Probing the methanol-assisted autocatalytic formation of methanol over Cu/ZnO/Al2O3 by high-pressure methanol and methyl formate pulses

Abstract: Using high-pressure methanol and methyl formate pulses as a surface-sensitive operando method for high-pressure methanol synthesis over Cu/ZnO/Al2O3, the recently found autocatalytic pathway was confirmed. The autocatalytic effect is assumed...

Cited by 3 publications

References 38 publications

CO2 Hydrogenation to CH3OH over Cu‐Based Catalysts: Primary and Side Reactions

CO2 Hydrogenation to CH3OH over Cu‐Based Catalysts: Primary and Side Reactions

The Enigma of Methanol Synthesis by Cu/ZnO/Al2O3-Based Catalysts

Effect of hydrothermal environment on Cu-ZnO/Al2O3 catalyst for hydrogenation of CO2 to methanol

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Probing the methanol-assisted autocatalytic formation of methanol over Cu/ZnO/Al₂O₃ by high-pressure methanol and methyl formate pulses

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

CO₂ Hydrogenation to CH₃OH over Cu‐Based Catalysts: Primary and Side Reactions

The Enigma of Methanol Synthesis by Cu/ZnO/Al₂O₃-Based Catalysts