Skip to main content

Advertisement

SpringerLink
Log in

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

  • Original Paper
  • Published:
Clean Technologies and Environmental Policy Aims and scope Submit manuscript

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.

Graphical abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14
Fig. 15
Fig. 16
Fig. 17
Fig. 18
Fig. 19
Fig. 20
Fig. 21
Fig. 22
Fig. 23
Fig. 24
Fig. 25
Fig. 26
Fig. 27
Fig. 28
Fig. 29
Fig. 30
Fig. 31
Fig. 32
Fig. 33

Similar content being viewed by others

Data availability

Enquiries about data availability should be directed to the authors.

Abbreviations

AARD:

Average absolute relative deviation

[BMIm][BF4]:

1-Butyl-3-methylimidazolium tetrafluoroborate

[BMIm][PF6]:

1-Butyl-3-methylimidazolium hexafluorophosphate

[BMIm][NTf2]:

1-Butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

[BMIm][Ac]:

1-Butyl-3-methylimidazolium acetate

FTS:

Fischer–Tropsch synthesis

GC:

Group contribution

ILs:

Ionic liquids

LLE:

Liquid–liquid equilibrium

PSRK:

Predictive Soave–Redlich–Kwong equation of State

RMSE:

Root-mean-square error

RWGS:

Reverse water–gas shift

UNIFAC:

Universal Functional-Group Activity Coefficient Model

UNIQUAC:

Universal quasi-chemical model

VLE:

Vapor–liquid equilibrium

\(\omega_{i}\) :

Acentric factor of component i

\(\gamma_{i}\) :

Activity coefficient of component i in the mixture

\(\alpha_{i} \left( T \right)\) :

Alpha function

\(R^{2}\) :

Coefficient of determination

\(P_{{{\text{c}}_{i} }}\) :

Critical pressure of component i

\(T_{{{\text{c}}_{i} }}\) :

Critical temperature of component i

\(G^{{\text{E}}}\) :

Excess Gibbs energy

\(v_{{\text{m}}}\) :

Molar volume of component i

References

Download references

Acknowledgements

The authors gratefully acknowledge REPSOL Sinopec Brasil for its financial and technical support and ANP (Brazilian National Agency for Petroleum, Natural Gas and Biofuels) for the strategic importance of its support through the R&D levy regulation. The authors also acknowledge the São Paulo Research Foundation (FAPESP) (#2021/07155-6) and the National Council for Scientific and Technological Development—CNPQ (#314598/2021-9, # 155735/2022-5). This study was financed in part by The Coordination for the Improvement of Higher Education Personnel (CAPES), Brazil—Finance Code 001.

Author information

Authors and Affiliations

  1. Universidade de São Paulo, Escola Politécnica, São Paulo, Brazil

    Valdeir A. Abreu, Murilo L. Alcantara, Newton L. Ferreira, Antônio E. Bresciani, Cláudio A. O. Nascimento & Rita M. B. Alves

  2. Repsol Sinopec Brasil, Rio de Janeiro, Brazil

    Gabriel S. Bassani

Authors
  1. Valdeir A. Abreu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Murilo L. Alcantara
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Newton L. Ferreira
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Antônio E. Bresciani
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Gabriel S. Bassani
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Cláudio A. O. Nascimento
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Rita M. B. Alves
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

VAA contributed to methodology, formal analysis, investigation, and writing original; MLA contributed to methodology, formal analysis, supervision, and writing & review; NLF contributed to software support; AEB contributed to formal analysis and review; CAON contributed to conceptualization and resources; GSB contributed to review and resources; RMBA contributed to methodology, resources, formal analysis, writing & review, and supervision.

Corresponding author

Correspondence to Rita M. B. Alves.

Ethics declarations

Competing interests

The authors declare no competing interests.

Declarations

The authors declare that they have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 1225 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Abreu, V.A., Alcantara, M.L., Ferreira, N.L. et al. Thermodynamic insights on the influence of ionic liquids on the reverse water–gas shift reaction. Clean Techn Environ Policy 26, 197–215 (2024). https://doi.org/10.1007/s10098-023-02652-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10098-023-02652-7

Keywords

Search

Navigation