High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics

Mahinder Ramdin, Andrew R.T. Morrison, Mariette De Groen, Rien Van Haperen, Robert De Kler, Erdem Irtem, Antero T. Laitinen, Leo J.P. Van Den Broeke, Tom Breugelmans, J. P.Martin Trusler, Wiebren De Jong, Thijs J.H. Vlugt (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

Abstract

We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low-pH (i.e., pH < pKa) electrolyte solutions. The effects of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (?80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ?30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

Original languageEnglish
Pages (from-to)22718-22740
JournalIndustrial and Engineering Chemistry Research
Volume58
Issue number51
DOIs
Publication statusPublished - 2019
MoE publication typeA1 Journal article-refereed

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formic acid
Formic acid
Economics
Electrolytes
Current density
Electrodialysis
Acids
Electrocatalysts
Liquids

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Ramdin, Mahinder ; Morrison, Andrew R.T. ; De Groen, Mariette ; Van Haperen, Rien ; De Kler, Robert ; Irtem, Erdem ; Laitinen, Antero T. ; Van Den Broeke, Leo J.P. ; Breugelmans, Tom ; Trusler, J. P.Martin ; Jong, Wiebren De ; Vlugt, Thijs J.H. / High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate : Effect of pH on the Downstream Separation Process and Economics. In: Industrial and Engineering Chemistry Research. 2019 ; Vol. 58, No. 51. pp. 22718-22740.
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title = "High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics",
abstract = "We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low-pH (i.e., pH < pKa) electrolyte solutions. The effects of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (?80{\%}) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ?30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.",
author = "Mahinder Ramdin and Morrison, {Andrew R.T.} and {De Groen}, Mariette and {Van Haperen}, Rien and {De Kler}, Robert and Erdem Irtem and Laitinen, {Antero T.} and {Van Den Broeke}, {Leo J.P.} and Tom Breugelmans and Trusler, {J. P.Martin} and Jong, {Wiebren De} and Vlugt, {Thijs J.H.}",
year = "2019",
doi = "10.1021/acs.iecr.9b03970",
language = "English",
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Ramdin, M, Morrison, ART, De Groen, M, Van Haperen, R, De Kler, R, Irtem, E, Laitinen, AT, Van Den Broeke, LJP, Breugelmans, T, Trusler, JPM, Jong, WD & Vlugt, TJH 2019, 'High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate: Effect of pH on the Downstream Separation Process and Economics', Industrial and Engineering Chemistry Research, vol. 58, no. 51, pp. 22718-22740. https://doi.org/10.1021/acs.iecr.9b03970

High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate : Effect of pH on the Downstream Separation Process and Economics. / Ramdin, Mahinder; Morrison, Andrew R.T.; De Groen, Mariette; Van Haperen, Rien; De Kler, Robert; Irtem, Erdem; Laitinen, Antero T.; Van Den Broeke, Leo J.P.; Breugelmans, Tom; Trusler, J. P.Martin; Jong, Wiebren De; Vlugt, Thijs J.H. (Corresponding Author).

In: Industrial and Engineering Chemistry Research, Vol. 58, No. 51, 2019, p. 22718-22740.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - High-Pressure Electrochemical Reduction of CO2 to Formic Acid/Formate

T2 - Effect of pH on the Downstream Separation Process and Economics

AU - Ramdin, Mahinder

AU - Morrison, Andrew R.T.

AU - De Groen, Mariette

AU - Van Haperen, Rien

AU - De Kler, Robert

AU - Irtem, Erdem

AU - Laitinen, Antero T.

AU - Van Den Broeke, Leo J.P.

AU - Breugelmans, Tom

AU - Trusler, J. P.Martin

AU - Jong, Wiebren De

AU - Vlugt, Thijs J.H.

PY - 2019

Y1 - 2019

N2 - We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low-pH (i.e., pH < pKa) electrolyte solutions. The effects of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (?80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ?30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

AB - We use a high-pressure semicontinuous batch electrochemical reactor with a tin-based cathode to demonstrate that it is possible to efficiently convert CO2 to formic acid (FA) in low-pH (i.e., pH < pKa) electrolyte solutions. The effects of CO2 pressure (up to 50 bar), bipolar membranes, and electrolyte (K2SO4) concentration on the current density (CD) and the Faraday efficiency (FE) of formic acid were investigated. The highest FE (?80%) of FA was achieved at a pressure of around 50 bar at a cell potential of 3.5 V and a CD of ?30 mA/cm2. To suppress the hydrogen evolution reaction (HER), the electrochemical reduction of CO2 in aqueous media is typically performed at alkaline conditions. The consequence of this is that products like formic acid, which has a pKa of 3.75, will almost completely dissociate into the formate form. The pH of the electrolyte solution has a strong influence not only on the electrochemical reduction process of CO2 but also on the downstream separation of (dilute) acid products like formic acid. The selection of separation processes depends on the dissociation state of the acids. A review of separation technologies for formic acid/formate removal from aqueous dilute streams is provided. By applying common separation heuristics, we have selected liquid-liquid extraction and electrodialysis for formic acid and formate separation, respectively. An economic evaluation of both separation processes shows that the formic acid route is more attractive than the formate one. These results urge for a better design of (1) CO2 electrocatalysts that can operate at low pH without affecting the selectivity of the desired products and (2) technologies for efficient separation of dilute products from (photo)electrochemical reactors.

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DO - 10.1021/acs.iecr.9b03970

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