Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling

Loukas Kollias; Manh Thuong Nguyen; Sarah I. Allec; Deepika Malhotra; Difan Zhang; Roger Rousseau; Vassiliki Alexandra Glezakou; Phillip K. Koech; David J. Heldebrant

doi:10.1021/acs.iecr.4c01143

Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling

Loukas Kollias
, Manh Thuong Nguyen
, Sarah I. Allec
, Deepika Malhotra
, Difan Zhang
, Roger Rousseau
, Vassiliki Alexandra Glezakou
, Phillip K. Koech
, David J. Heldebrant

Chemical Sciences Division

Research output: Contribution to journal › Article › peer-review

Abstract

Nitrogen oxides, present in flue gas, can cause negative impacts on amine carbon capture solvents by the formation of heat-stable salts and suspected carcinogens. Thus, to maximize the performance of water-lean solvents, a better understanding of this process in these systems is necessary. Here, a computational study for the fixation of the CO₂ capture solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) to nitramine/nitrosamine was conducted. The first step involves the dissociation of the NH bond of EEMPA, in which the homolytic mechanism is energetically more favorable than the heterolytic mechanism. The second step involves radical recombination to form N-N bonds. While NO₂ directly reacts with EEMPA, NO has almost no effect. However, in the presence of O₂, fixation of EEMPA by NO is enhanced via the formation of N₂O₄ species. Low reaction energies indicate that the formation of nitramine/nitrosamine may be a reversible process, suggesting that EEMPA could be recovered under thermal stripping conditions.

Original language	English
Pages (from-to)	12316-12324
Number of pages	9
Journal	Industrial and Engineering Chemistry Research
Volume	63
Issue number	28
DOIs	https://doi.org/10.1021/acs.iecr.4c01143
State	Published - Jul 17 2024

Funding

This work was supported by the U.S. Department of Energy, Office of Fossil Energy, FWP 77217 (managed by National Energy Technology Laboratory). M.-T.N. was also supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, project 81462 (Harnessing Confinement Effects, Stimuli, and Reactive Intermediates in Separations). PNNL is operated by Battelle for the U.S. Department of Energy under Contract DE-AC05-76RL01830. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231.

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title = "Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling",

abstract = "Nitrogen oxides, present in flue gas, can cause negative impacts on amine carbon capture solvents by the formation of heat-stable salts and suspected carcinogens. Thus, to maximize the performance of water-lean solvents, a better understanding of this process in these systems is necessary. Here, a computational study for the fixation of the CO2 capture solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) to nitramine/nitrosamine was conducted. The first step involves the dissociation of the NH bond of EEMPA, in which the homolytic mechanism is energetically more favorable than the heterolytic mechanism. The second step involves radical recombination to form N-N bonds. While NO2 directly reacts with EEMPA, NO has almost no effect. However, in the presence of O2, fixation of EEMPA by NO is enhanced via the formation of N2O4 species. Low reaction energies indicate that the formation of nitramine/nitrosamine may be a reversible process, suggesting that EEMPA could be recovered under thermal stripping conditions.",

author = "Loukas Kollias and Nguyen, \{Manh Thuong\} and Allec, \{Sarah I.\} and Deepika Malhotra and Difan Zhang and Roger Rousseau and Glezakou, \{Vassiliki Alexandra\} and Koech, \{Phillip K.\} and Heldebrant, \{David J.\}",

note = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society.",

year = "2024",

month = jul,

day = "17",

doi = "10.1021/acs.iecr.4c01143",

language = "English",

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T1 - Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling

AU - Kollias, Loukas

AU - Nguyen, Manh Thuong

AU - Allec, Sarah I.

AU - Malhotra, Deepika

AU - Zhang, Difan

AU - Rousseau, Roger

AU - Glezakou, Vassiliki Alexandra

AU - Koech, Phillip K.

AU - Heldebrant, David J.

PY - 2024/7/17

Y1 - 2024/7/17

N2 - Nitrogen oxides, present in flue gas, can cause negative impacts on amine carbon capture solvents by the formation of heat-stable salts and suspected carcinogens. Thus, to maximize the performance of water-lean solvents, a better understanding of this process in these systems is necessary. Here, a computational study for the fixation of the CO2 capture solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) to nitramine/nitrosamine was conducted. The first step involves the dissociation of the NH bond of EEMPA, in which the homolytic mechanism is energetically more favorable than the heterolytic mechanism. The second step involves radical recombination to form N-N bonds. While NO2 directly reacts with EEMPA, NO has almost no effect. However, in the presence of O2, fixation of EEMPA by NO is enhanced via the formation of N2O4 species. Low reaction energies indicate that the formation of nitramine/nitrosamine may be a reversible process, suggesting that EEMPA could be recovered under thermal stripping conditions.

AB - Nitrogen oxides, present in flue gas, can cause negative impacts on amine carbon capture solvents by the formation of heat-stable salts and suspected carcinogens. Thus, to maximize the performance of water-lean solvents, a better understanding of this process in these systems is necessary. Here, a computational study for the fixation of the CO2 capture solvent N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (EEMPA) to nitramine/nitrosamine was conducted. The first step involves the dissociation of the NH bond of EEMPA, in which the homolytic mechanism is energetically more favorable than the heterolytic mechanism. The second step involves radical recombination to form N-N bonds. While NO2 directly reacts with EEMPA, NO has almost no effect. However, in the presence of O2, fixation of EEMPA by NO is enhanced via the formation of N2O4 species. Low reaction energies indicate that the formation of nitramine/nitrosamine may be a reversible process, suggesting that EEMPA could be recovered under thermal stripping conditions.

UR - https://www.scopus.com/pages/publications/85199000667

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DO - 10.1021/acs.iecr.4c01143

M3 - Article

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SN - 0888-5885

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EP - 12324

JO - Industrial and Engineering Chemistry Research

JF - Industrial and Engineering Chemistry Research

IS - 28

ER -

Molecular Understanding of Nitrogen Oxide Fixation of Water-Lean Carbon Capture Solvents by Atomistic Modeling

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