Factors affecting primary and secondary pathways in CO2 hydrogenation to methanol over CuZnIn/MZrOx (La, Ti or Y)

Ortner, Nils; Lund, Henrik; Armbruster, Udo; Wohlrab, Sebastian; Kondratenko, Evgenii V.

doi:10.1016/j.cattod.2021.05.008

Cited by 12 publications

(13 citation statements)

References 29 publications

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“…Cu- − or In-containing − catalysts are typically applied for the CO 2 hydrogenation to CH 3 OH. The ongoing research in this field is focused on improving catalyst activity and/or the selectivity to CH 3 OH through designing materials possessing certainly structured CuO x or InO x species with different promoters. − There are only a few studies reporting CH 3 OH selectivity above 80% at CO 2 conversion above 5%.…”

Section: Introductionmentioning

confidence: 99%

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

et al. 2022

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CO2 hydrogenation to methanol (CH3OH) is widely accepted to proceed through two parallel reactions: (i) CH3OH formation and (ii) the reverse water gas shift (RWGS) reaction to CO. The latter reaction causes the loss of CH3OH selectivity. Our spatially resolved analysis of rates of product formation over a classical CuZnAlO x catalyst in a broad range of CO2 conversion degrees (from 0 to 90% of equilibrium conversion) suggests revisiting this concept. In comparison with the RWGS reaction, CH3OH decomposition to CO mainly contributes to the loss of CH3OH selectivity with a rising degree of CO2 conversion. Separate CH3OH decomposition tests in a broad range of experimental conditions proved that this side reaction is accelerated by H2O but negatively affected by H2 and rising total pressure. Moreover, the decomposition should occur on other sites rather than those participating in CH3OH synthesis from CO2 and can be practically suppressed above certain partial pressures of CH3OH and H2O due to site saturation. The sites responsible for the hydrogenation of CO2 to CH3OH, however, are not saturated. Thus, this product can be further produced in downstream catalyst layers. As this concept is valid for several CuZn-based catalysts, we provide fundamentals for the design of selective CH3OH synthesis catalysts and for optimizing reaction conditions. Operating under conditions, where the undesired CH3OH decomposition reaction is hindered, enabled us to achieve 93% CH3OH selectivity at 19% CO2 conversion (55% equilibrium conversion) at 50 bar and 200 °C using a feed with the ratio of H2/CO2 of 3.

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Section: Introductionmentioning

confidence: 99%

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

et al. 2022

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“…This underscores the potential of CZ-OGbased catalysts in suppressing secondary reactions, such as further decomposition of CH 3 OH to CO, which leads to decreased CH 3 OH selectivity at elevated CO 2 conversion levels. 27 Intriguingly, the DRIFT spectra for methanol adsorption on either pristine or Culoaded ZrO 2 -AC supports within a temperature range of 50-230 1C not only reveal prominent vibration bands around 2930 and 2820 cm À1 , corresponding to the stretching mode of methoxy species, but also bands around 1586 cm À1 , attributed to the stretching mode of formate species (Fig. 3d and Fig.…”

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confidence: 88%

Oxygen vacancy promoted carbon dioxide activation over Cu/ZrO₂for CO₂-to-methanol conversion

et al. 2023

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“…Recently, Kondratenko et al investigated the influence of methanol decomposition, occurring at higher conversion levels, on the selectivity of CO 2 hydrogenation to methanol over CZA catalysts as a function of conversion. − Building on classical approaches to kinetic studies, the researchers investigated a large range of CO 2 conversion levels under otherwise fixed process conditions by varying the amount of catalyst and space velocities . The central question they sought to look into was whether the consecutive decomposition of methanol occurs at rates relevant to the overall production of methanol.…”

Section: –2022mentioning

confidence: 99%

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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Factors affecting primary and secondary pathways in CO2 hydrogenation to methanol over CuZnIn/MZrOx (La, Ti or Y)

Cited by 12 publications

References 29 publications

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Oxygen vacancy promoted carbon dioxide activation over Cu/ZrO₂for CO₂-to-methanol conversion

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

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Factors affecting primary and secondary pathways in CO2 hydrogenation to methanol over CuZnIn/MZrOx (La, Ti or Y)

Cited by 12 publications

References 29 publications

Revealing Origins of Methanol Selectivity Loss in CO2 Hydrogenation over CuZn-Containing Catalysts

Revealing Origins of Methanol Selectivity Loss in CO2 Hydrogenation over CuZn-Containing Catalysts

Oxygen vacancy promoted carbon dioxide activation over Cu/ZrO2for CO2-to-methanol conversion

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

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Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Revealing Origins of Methanol Selectivity Loss in CO₂ Hydrogenation over CuZn-Containing Catalysts

Oxygen vacancy promoted carbon dioxide activation over Cu/ZrO₂for CO₂-to-methanol conversion

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