IMPACTS OF KEY DEGRADATION BYPRODUCTS ON AMINE SCRUBBING FOR POST-COMBUSTION CARBON CAPTURE

Author

Thomas Jorgensen, University of KentuckyFollow

Author ORCID Identifier

https://orcid.org/0000-0001-9662-5619

Date Available

1-15-2025

Year of Publication

2024

Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation

College

Arts and Sciences

Department/School/Program

Chemistry

First Advisor

Marcelo I. Guzman

Second Advisor

Jesse G. Thompson

Abstract

The increasing atmospheric CO₂ concentration causes significant concern about global warming and its environmental impact. Industrial sectors, including power generation, transportation, and production factories, contribute most of the anthropogenic sources of CO₂ emissions. Researchers search for methods to mitigate these CO₂ emissions without compromising the benefits of industrial processes, including CO₂ capture, utilization, and sequestration (CCUS). Post-combustion carbon capture (PCCC) by amine scrubbing is the most technology ready CCUS, with various pilot-scale projects worldwide showing small-scale to fully operational plants. While researchers have made significant progress in amine scrubbing, they strive to improve the efficiency and economics of these plants. One challenge they face includes solvent degradation due to flue gas constituents and temperature effects. This dissertation focuses on the degradation byproducts' impact on the parent amine solvent. It explores knowledge about degradation byproducts in amine solvents used in carbon capture, including what degradation products, how much, how they form, and what impact these products have on the capture process. The dissertation splits into three sections where the first focuses on three thermal degradation byproducts of ethanolamine (MEA): oxazolidine-2-one (OZD), N-(2-hydroxyethyl)-ethylenediamine (HEEDA), and N-(2-hydroxyethyl)-imidazoline-2-one (HEIA) interactions in the solvent. The second focuses on O₂ solubility and the role O₂ plays in oxidative degradation. The final section discusses some initial degradation results of a new class of amine carbon capture solvents called water-lean (WL) solvents. The discussion of the thermal degradation byproducts began by describing thermal degradation byproducts that react with CO₂ with and without the parent amine present. The species found were explored further at the liquid-vapor barrier to explain how the species interact with each other. The degradation byproducts with unhindered primary or secondary amines, such as HEEDA, create a pseudo-blended solvent that could improve the solvent's capture performance as it improves the CO₂ solubility in the amine solvents. In contrast, hindered structures like HEIA and OZD will minimally impact the speciation in the amine solvents. However, these species revert to the carbamate at lower CO₂ concentrations or higher temperatures and further react with CO₂ concentrations. The discussion on O₂ solubility in the different amine solvents and the role O₂ plays in oxidative degradation began by validating a dissolved oxygen (DO) electrochemical probe by redox titrations following the Winkler method. The validated probe then measured the DO or O₂ solubility in different amine solutions under various conditions found in CO₂ capture. It also explored how additives used in advanced amine solvents impact the O₂ solubility in the solution. The redox titration measured the DO slightly higher than the probe, validating the electrochemical probe for amine solvents. However, solvents with transition metals that can oxidize iodine cannot use this method to measure the DO in the solvents. In the amine solvents, the diamines measured higher O₂ solubility than the alkanolamines, and the alkanolamines measured higher O₂ solubility than the amine diols. In addition, as the number of hydrogens bonded to nitrogen decreased, the O₂ solubility decreased. The ionic effect on O₂ was also demonstrated, where the DO decreased with increased CO₂ loading. However, there was still DO, indicating that the solvents will undergo oxidative degradation at high loadings. Furthermore, the solvents minimally impacted the O₂ solubility except those that can react with CO₂. The additive 2-mercaptobenzathiazole (MBT) decreased the DO concentration until it exhausted its capacity to react with O₂, and then the DO rose back to the levels at equilibrium. The additive sodium metavanadate increased the DO concentration because metavanadate can react with O₂, increasing the oxidative potential in the solution. The final section described the initial findings of degradation byproducts of WL solvents and what the organic cosolvent does in the system, including some initial discussions on how the organic cosolvent impacts an amine solvent, how the solvent phase separates at higher loadings due to an ionic effect in the cosolvent, and what compounds were found during oxidative degradation experiments.

Digital Object Identifier (DOI)

https://doi.org/10.13023/etd.2024.262

Recommended Citation

Jorgensen, Thomas, "IMPACTS OF KEY DEGRADATION BYPRODUCTS ON AMINE SCRUBBING FOR POST-COMBUSTION CARBON CAPTURE" (2024). Theses and Dissertations--Chemistry. 197.
https://uknowledge.uky.edu/chemistry_etds/197