US EPA

999686 

Journal Article 

Tandem mass spectrometry measurement of the collision products of carbamate anions derived from CO2 capture sorbents: paving the way for accurate quantitation 

Jackson, P; Fisher, KJ; Attalla, MI 

2011 

1 

Journal of the American Society for Mass Spectrometry
ISSN: 1044-0305
EISSN: 1879-1123 

SPRINGER 

NEW YORK 

22 

8 

1420-1431 

English 

21953197 

10.1007/s13361-011-0161-5 

WOS:000293029600016 

https://pubs.acs.org/doi/10.1021/jasms.8b04092
Exit
 

The reaction between CO(2) and aqueous amines to produce a charged carbamate product plays a crucial role in post-combustion capture chemistry when primary and secondary amines are used. In this paper, we report the low energy negative-ion CID results for several anionic carbamates derived from primary and secondary amines commonly used as post-combustion capture solvents. The study was performed using the modern equivalent of a triple quadrupole instrument equipped with a T-wave collision cell. Deuterium labeling of 2-aminoethanol (1,1,2,2,-d(4)-2-aminoethanol) and computations at the M06-2X/6-311++G(d,p) level were used to confirm the identity of the fragmentation products for 2-hydroxyethylcarbamate (derived from 2-aminoethanol), in particular the ions CN(-), NCO(-) and facile neutral losses of CO(2) and water; there is precedent for the latter in condensed phase isocyanate chemistry. The fragmentations of 2-hydroxyethylcarbamate were generalized for carbamate anions derived from other capture amines, including ethylenediamine, diethanolamine, and piperazine. We also report unequivocal evidence for the existence of carbamate anions derived from sterically hindered amines (Tris(2-hydroxymethyl)aminomethane and 2-methyl-2-aminopropanol). For the suite of carbamates investigated, diagnostic losses include the decarboxylation product (-CO(2), 44 mass units), loss of 46 mass units and the fragments NCO(-) (m/z 42) and CN(-) (m/z 26). We also report low energy CID results for the dicarbamate dianion ((-)O(2)CNHC(2)H(4)NHCO(2)(-)) commonly encountered in CO(2) capture solution utilizing ethylenediamine. Finally, we demonstrate a promising ion chromatography-MS based procedure for the separation and quantitation of aqueous anionic carbamates, which is based on the reported CID findings. The availability of accurate quantitation methods for ionic CO(2) capture products could lead to dynamic operational tuning of CO(2) capture-plants and, thus, cost-savings via real-time manipulation of solvent regeneration energies. 

Amines; Carbamate anion; Post-combustion capture; Aminomethane; Carbamate anion; Collision cells; Collision products; Condensed phase; Cost saving; Deuterium labeling; Dianions; Diethanolamine; Ethylene diamine; Low energies; Neutral loss; Post-combustion; Post-combustion capture; Primary and secondary amine; Regeneration energy; Tandem mass spectrometry; Triple quadrupole; Amines; Carboxylation; Chromatography; Combustion; Deuterium; Ion chromatography; Mass spectrometry; Methanol; Negative ions; Carbon dioxide; 2 hydroxyethylcarbamate; 2 methyl 2 aminopropanol; amine; anion; carbamate anion; carbamic acid derivative; carbon dioxide; diethanolamine; ethylenediamine; isocyanate; piperazine; solvent; tris(2 hydroxymethyl)aminomethane; unclassified drug; water; article; chemical analysis; chemical phenomena; collisionally activated dissociation; decarboxylation; fragmentation reaction; isotope labeling; mathematical analysis; post combustion capture; quantitative analysis; tandem mass spectrometry