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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 - J. Am. Soc. Mass Spectrom. (2011)

Bottom Line: 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.

View Article: PubMed Central - PubMed

Affiliation: Coal Portfolio-CSIRO Energy, Newcastle, NSW, Australia.

ABSTRACT
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.

No MeSH data available.


Related in: MedlinePlus

CO2 capture amines for which chemistry with bicarbonate (specifically carbamate formation) was investigated. 1 = 2-aminoethanol (ethanolamine, MEA); 2 = 1,2-diaminoethane (ethylenediamine, EN); 3 = piperazine (PZ); 4 = 2-amino-2-methyl-1-propanol (AMP); 5 = 2-amino-2-(hydroxymethyl)propane-1,3-diol (Tris); 6 = 2,2'-iminodiethanol (diethanolamine, DEA)
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Fig1: CO2 capture amines for which chemistry with bicarbonate (specifically carbamate formation) was investigated. 1 = 2-aminoethanol (ethanolamine, MEA); 2 = 1,2-diaminoethane (ethylenediamine, EN); 3 = piperazine (PZ); 4 = 2-amino-2-methyl-1-propanol (AMP); 5 = 2-amino-2-(hydroxymethyl)propane-1,3-diol (Tris); 6 = 2,2'-iminodiethanol (diethanolamine, DEA)

Mentions: The carbamate derivatives of capture amines were generated by mixing equimolar amounts (1–2 mmol) of the respective amine and NaHCO3 (Sigma, Sydney, Australia, 99.9%) in 15 mL charcoal-filtered water (R > 18 MΩ). The amines investigated and their structures are presented in Figure 1. Reagent purity: MEA (Sigma, Sydney, Australia, > 99%), EN (Sigma, Sydney, Australia, 99%), PZ (Sigma, Sydney, Australia, 99 %), AMP (Fluka, Sydney, Australia, 99%), DEA (Aldrich, Sydney, Australia,  > 99.5%), Tris (Sigma, Sydney, Australia, > 99%). The mixtures were then heated to 60 °C in a water bath for 2 h. The solutions were diluted appropriately before direct infusion into the mass spectrometer for CID experiments. 1,1,2,2-d4-2-Aminoethanol was purchased from CDN Isotopes (Sydney, Australia).Figure 1


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 - J. Am. Soc. Mass Spectrom. (2011)

CO2 capture amines for which chemistry with bicarbonate (specifically carbamate formation) was investigated. 1 = 2-aminoethanol (ethanolamine, MEA); 2 = 1,2-diaminoethane (ethylenediamine, EN); 3 = piperazine (PZ); 4 = 2-amino-2-methyl-1-propanol (AMP); 5 = 2-amino-2-(hydroxymethyl)propane-1,3-diol (Tris); 6 = 2,2'-iminodiethanol (diethanolamine, DEA)
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC3141848&req=5

Fig1: CO2 capture amines for which chemistry with bicarbonate (specifically carbamate formation) was investigated. 1 = 2-aminoethanol (ethanolamine, MEA); 2 = 1,2-diaminoethane (ethylenediamine, EN); 3 = piperazine (PZ); 4 = 2-amino-2-methyl-1-propanol (AMP); 5 = 2-amino-2-(hydroxymethyl)propane-1,3-diol (Tris); 6 = 2,2'-iminodiethanol (diethanolamine, DEA)
Mentions: The carbamate derivatives of capture amines were generated by mixing equimolar amounts (1–2 mmol) of the respective amine and NaHCO3 (Sigma, Sydney, Australia, 99.9%) in 15 mL charcoal-filtered water (R > 18 MΩ). The amines investigated and their structures are presented in Figure 1. Reagent purity: MEA (Sigma, Sydney, Australia, > 99%), EN (Sigma, Sydney, Australia, 99%), PZ (Sigma, Sydney, Australia, 99 %), AMP (Fluka, Sydney, Australia, 99%), DEA (Aldrich, Sydney, Australia,  > 99.5%), Tris (Sigma, Sydney, Australia, > 99%). The mixtures were then heated to 60 °C in a water bath for 2 h. The solutions were diluted appropriately before direct infusion into the mass spectrometer for CID experiments. 1,1,2,2-d4-2-Aminoethanol was purchased from CDN Isotopes (Sydney, Australia).Figure 1

Bottom Line: 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.

View Article: PubMed Central - PubMed

Affiliation: Coal Portfolio-CSIRO Energy, Newcastle, NSW, Australia.

ABSTRACT
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.

No MeSH data available.


Related in: MedlinePlus