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Clean Technologies and Environmental Policy

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24-11-2023 | Original Paper

Thermodynamic insights on the influence of ionic liquids on the reverse water–gas shift reaction

Authors: Valdeir A. Abreu, Murilo L. Alcantara, Newton L. Ferreira, Antônio E. Bresciani, Gabriel S. Bassani, Cláudio A. O. Nascimento, Rita M. B. Alves

Published in: Clean Technologies and Environmental Policy | Issue 1/2024

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Abstract

As global initiatives pivot toward more sustainable industrial processes, the conversion of carbon dioxide (CO₂) into high-value chemicals offers a promising path forward. Ionic liquids (ILs), in particular, show the potential in boosting the efficacy of related reactions. However, their thermodynamic influence on the chemical equilibrium of reactive processes requires further exploration. This study presents a detailed assessment of three specific ILs—[BMIm][BF₄], [BMIm][PF₆], and [BMIm][NTf₂]—on the equilibrium of the CO₂ hydrogenation to carbon monoxide (CO) via the Reverse Water–Gas Shift (RWGS) reaction. Both predictive and non-predictive methods based on the Predictive Soave–Redlich–Kwong equation of state were employed to represent the pure ILs’ densities and vapor pressure. The non-predictive approach provided a more accurate representation, further utilized for describing the phase equilibria of mixtures encompassing ILs, CO₂, H₂, CO, and H₂O. Through extensive evaluation, the effects of temperature, pressure, and IL content on CO₂ hydrogenation were elucidated. Results indicate that higher molar ratios of ILs amplify the equilibrium conversion. Additionally, the system sensitivity to pressure changes was observed, leading to enhanced CO₂ conversion at elevated pressures. With varying temperatures, systems containing hydrophobic ILs ([BMIm][PF₆] or [BMIm][NTf₂]) displayed increased conversion rates at high temperatures, while the hydrophilic IL [BMIm][BF₄] demonstrated superior CO production at lower temperatures. This behavior is linked to temperature’s profound influence on water sorption in the IL. Notably, the system with hydrophilic IL [BMIm][BF₄] exhibited a striking increase in CO₂ conversion, from 1.1 to 54.1% at 348 K and 2.0 MPa, almost 50-fold higher than the original conversion. This study illuminates the pivotal role of thermodynamics in driving the future of IL-based CO₂ conversion technology, highlighting the potential for further advancements in sustainable industry practices.

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Title: Thermodynamic insights on the influence of ionic liquids on the reverse water–gas shift reaction
Authors: Valdeir A. Abreu
Murilo L. Alcantara
Newton L. Ferreira
Antônio E. Bresciani
Gabriel S. Bassani
Cláudio A. O. Nascimento
Rita M. B. Alves
Publication date: 24-11-2023
Publisher: Springer Berlin Heidelberg
Published in: Clean Technologies and Environmental Policy / Issue 1/2024
Print ISSN: 1618-954X
Electronic ISSN: 1618-9558
DOI: https://doi.org/10.1007/s10098-023-02652-7

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