Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation


Arts and Sciences



First Advisor

Dr. John P. Selegue

Second Advisor

Dr. Dong-Sheng Yang


In the selection of candidates for CO2 absorption, solvent thermal degradation has become a general concern due to the significant impact on operational cost and the intention to use thermal compression from high temperature stripping to minimize the overall process energy. In this research, the impact of flue gas contaminants on Monoethanolamine (MEA) thermal degradation was investigated at elevated temperatures consistent with those in the CO2 stripper. Nitrite, fly ash, sulfate and thiosulfate were each added to 5.0 M MEA and the contaminant-containing MEA solutions were degraded at 125 °C, 135 °C and 145 °C. MEA degrades significantly more in the presence of nitrite (5000 ppm) than MEA alone at the same amine molar concentration for all three temperatures. MEA degradation activation energy of MEA-nitrite solution is approximately one-seventh of that of MEA solution without nitrite. Fly ash was observed to inhibit nitrite-induced MEA degradation and greatly increase the MEA degradation activation energy of MEA-nitrite solution. Fly ash, sodium sulfate and sodium thiosulfate by themselves were not shown to impact MEA thermal degradation rate.

Sodium salts of glycine, sarcosine, alanine and ß-alanine were thermally degraded at 125 °C, 135 °C and 145 °C, respectively, to discover the structural reasons for their thermal stability. These four amino acids have enhanced thermal degradation rates compared to MEA. The stability order for amino acid salts tested to date is: sarcosinate > alaninate > ß-alaninate. Calculated activation energies for the degradation processes are lower than that of MEA. ß-Alaninate (ß-Ala) thermal degradation generates ß-Ala dimer (major degradation product), ß-Ala dimer carbamate and tetrahydro-1,3-oxazin-6-one.

Functional groups, amine orders and steric effect were investigated for their impact on amine thermal degradation. Primary amines with chain structures showed a thermal stability trend as diamine > alkanolamine > amino acid salt. For alknolamine and diamine structural isomers, the primary amines are more stable than the secondary amines. Steric hindrance around the amine group plays a global positive role in protecting amines against thermal degradation.