Measurement of nitrosamine and nitramine formation from NOx reactions with amines during amine-based carbon dioxide capture for postcombustion carbon sequestration

Ning Dai, Amisha D. Shah, Lanhua Hu, Michael J. Plewa, Bruce McKague, William A. Mitch

Research output: Contribution to journalArticlepeer-review


With years of full-scale experience for precombustion CO2 capture, amine-based technologies are emerging as the prime contender for postcombustion CO2 capture. However, concerns for postcombustion applications have focused on the possible contamination of air or drinking water supplies downwind by potentially carcinogenic N-nitrosamines and N-nitramines released following their formation by NOx reactions with amines within the capture unit. Analytical methods for N-nitrosamines in drinking waters were adapted to measure specific N-nitrosamines and N-nitramines and total N-nitrosamines in solvent and washwater samples. The high levels of amines, aldehydes, and nitrite in these samples presented a risk for the artifactual formation of N-nitrosamines during sample storage or analysis. Application of a 30-fold molar excess of sulfamic acid to nitrite at pH 2 destroyed nitrite with no significant risk of artifactual nitrosation of amines. Analysis of aqueous morpholine solutions purged with different gas-phase NO and NO2 concentrations indicated that N-nitrosamine formation generally exceeds N-nitramine formation. The total N-nitrosamine formation rate was at least an order of magnitude higher for the secondary amine piperazine (PZ) than for the primary amines 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA) and the tertiary amine methyldiethanolamine (MDEA). Analysis of pilot washwater samples indicated a 59 μM total N-nitrosamine concentration for a system operated with a 25% AMP/15% PZ solvent, but only 0.73 μM for a 35% MEA solvent. Unfortunately, a greater fraction of the total N-nitrosamine signal was uncharacterized for the MEA-associated washwater. At a 0.73 μM total N-nitrosamine concentration, a ∼25000-fold reduction in concentration is needed between washwater units and downwind drinking water supplies to meet proposed permit limits.

Original languageEnglish (US)
Pages (from-to)9793-9801
Number of pages9
JournalEnvironmental Science and Technology
Issue number17
StatePublished - Sep 4 2012

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry


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