Highly effective hydrogenation of CO2 to methanol over Cu/ZnO/Al2O3 catalyst: A process economy &amp; environmental aspects

Yusuf, Noor; Almomani, Fares

doi:10.1016/j.fuel.2022.126027

Cited by 45 publications

(21 citation statements)

References 48 publications

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“…Reading this short review article can be considered a starting point. It should also be mentioned that other important topics, such as kinetic or engineering aspects of the process, − are not discussed at all, nor are discussed the potentialities of alternative catalysts, despite the fact that several solutions have been proposed over the years, Figure …”

Section: Introductionmentioning

confidence: 99%

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Pacchioni

2024

ACS Catal.

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For more than half a century, the industrial production of methanol in the world has been based on a heterogeneous Cu/ ZnO/Al 2 O 3 catalyst where Cu nanoparticles are dispersed on an alumina support with ZnO particles as promoters. The reaction starts with syngas, a mixture of CO, CO 2 , and hydrogen, and the hydrogenation of carbon dioxide is an essential part of the process. Despite the technological importance and the high number of studies dedicated to identifying the structure of the functioning catalyst, there are still several open questions on the nature of the active sites and phases. Over the years, various hypotheses have been formulated. The most accredited versions concern the formation of CuZn alloys, the migration of ZnO over the Cu nanoparticles which become covered by an ultrathin oxide layer, and the role of the Cu−ZnO interface and, in particular, of the presence of Cu + ions. The role of alumina as a promoter has also been widely discussed, suggesting that the oxide provides acidic sites where intermediates are stabilized or that Al dopants enter the ZnO phase, altering its properties. The reality, as discussed in this brief overview, is that all these mechanisms are probably contributing but under different conditions of temperature, pressure, and reagent composition. This results in a dynamic catalyst that makes unambiguous identification of active sites difficult, if not impossible. Less controversial is the reaction mechanism, although even in this case the path followed by the reaction is a delicate function of various conditions, including the composition of the reaction mixture and the presence of water or other contaminants.

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Section: Introductionmentioning

confidence: 99%

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Pacchioni

2024

ACS Catal.

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“…The processes of methanol/DME synthesis from CO 2 and the conversion of oxygenates to hydrocarbons have reached considerable level and technological development. − Similarly, the conversion of methanol to hydrocarbons has also progressed. − However, the optimal conditions for the integrated process differ from those of the individual reaction stages. Moreover, the composition of the reaction medium is also different.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Model for the Direct Conversion of CO₂/CO into Light Olefins over an In₂O₃–ZrO₂/SAPO-34 Tandem Catalyst

Portillo,

Parra,

Aguayo

et al. 2024

ACS Sustainable Chem. Eng.

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An original kinetic model is proposed for the direct production of light olefins by hydrogenation of CO 2 /CO (CO x ) mixtures over an In 2 O 3 −ZrO 2 /SAPO-34 tandem catalyst, quantifying deactivation by coke. The reaction network comprises 12 individual reactions, and deactivation is quantified with expressions dependent on the concentration of methanol (as coke precursor) and H 2 O and H 2 (as agents attenuating coke formation). The experimental results were obtained in a fixed-bed reactor under the following conditions: In 2 O 3 −ZrO 2 /SAPO-34 mass ratio, 0/1−1/0; 350−425 °C; 20−50 bar; H 2 /CO x ratio, 1−3; CO 2 /CO x ratio, 0−1; space time, 0−10 g In2O3−ZrO2 h mol C −1 , 0−20 g SAPO-34 h mol C −1; time, up to 500 h; H 2 O and CH 3 OH in the feed, up to 5% vol. The utility of the model for further scale-up studies is demonstrated by its application in optimizing the process variables (temperature, pressure, and CO 2 /CO x ratio). The model predicts an olefin yield higher than 7% (selectivity above 60%), a CO x conversion of 12% and a CO 2 conversion of 16% at 415 °C and 50 bar, for a CO 2 /CO x = 0.5 in the feed. Additionally, an analysis of the effect of In 2 O 3 −ZrO 2 and SAPO-34 loading in the configuration of the tandem catalyst is conducted, yielding 17% olefins and complete conversion of CO 2 under full water removal conditions.

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“…1 Additionally, CO 2 can also be regarded as a renewable C1 resource due to its inherent characteristics such as nontoxicity, low cost, abundant reserves, easy accessibility, etc. 2 Thus, various value-added chemicals and fuels including methanol, 3 hydrocarbons, 4 cyclic carbonates, 5 quinazolinediones, 6 amides 7 and others have been produced using CO 2 as a C1 feedstock, which offer green reaction routes for these organic syntheses from the viewpoint of green chemistry and sustainable development. However, since CO 2 is thermodynamically stable and kinetically inert, metal catalysts and harsh reaction conditions are generally required for its transformation.…”

Section: Introductionmentioning

confidence: 99%

Benoxazolone-based ionic liquid catalyzed C–S bond construction for synthesis of benzothiazoles from 2-aminothiophenols and CO₂ under ambient conditions

Gao,

Zhao,

Gao

et al. 2023

New J. Chem.

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Highly effective hydrogenation of CO2 to methanol over Cu/ZnO/Al2O3 catalyst: A process economy & environmental aspects

Cited by 45 publications

References 48 publications

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Kinetic Model for the Direct Conversion of CO₂/CO into Light Olefins over an In₂O₃–ZrO₂/SAPO-34 Tandem Catalyst

Benoxazolone-based ionic liquid catalyzed C–S bond construction for synthesis of benzothiazoles from 2-aminothiophenols and CO₂ under ambient conditions

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Highly effective hydrogenation of CO2 to methanol over Cu/ZnO/Al2O3 catalyst: A process economy & environmental aspects

Cited by 45 publications

References 48 publications

From CO2 to Methanol on Cu/ZnO/Al2O3 Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

From CO2 to Methanol on Cu/ZnO/Al2O3 Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Kinetic Model for the Direct Conversion of CO2/CO into Light Olefins over an In2O3–ZrO2/SAPO-34 Tandem Catalyst

Benoxazolone-based ionic liquid catalyzed C–S bond construction for synthesis of benzothiazoles from 2-aminothiophenols and CO2 under ambient conditions

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Product

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From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

From CO₂ to Methanol on Cu/ZnO/Al₂O₃ Industrial Catalyst. What Do We Know about the Active Phase and the Reaction Mechanism?

Kinetic Model for the Direct Conversion of CO₂/CO into Light Olefins over an In₂O₃–ZrO₂/SAPO-34 Tandem Catalyst

Benoxazolone-based ionic liquid catalyzed C–S bond construction for synthesis of benzothiazoles from 2-aminothiophenols and CO₂ under ambient conditions