Thermal degradation of PZ-promoted tertiary amines for CO2 capture

The thermal degradation of piperazine (PZ)-promoted tertiary amine solvents for CO2-capture has been investigated and quantified in this study, which takes place in the high temperature (>100 °C) section of the capture plant. PZ-promoted tertiary amine solvents possess comparable energy performance to concentrated PZ, considered a benchmark solvent for CO2 capture from flue gas without its solid solubility limits that hinder operational performance. PZ-promoted aliphatic tertiary amine solvents with at least one methyl group, such as methyldiethanolamine (MDEA), were found to be the least stable solvents and can be regenerated in the desorber between 120 and 130 °C. PZ-promoted tertiary amine solvents with no methyl groups, such as ethyldiethanolamine (EDEA), were found to have an intermediate stability and can be regenerated in the desorber between 130 and 140 °C. PZ-promoted tertiary morpholines, such as hydroxyethylmorpholine (HEM), were found to be stable above 150 °C. Tertiary amines with at least one hydroxyethyl or hydroxyisopropyl functional group form intermediate byproducts that can accelerate the degradation rate of the promoter by a factor from 1.5 to 2.3. Tertiary amines with 3-carbon and 5-carbon functional groups, such as dimethylaminopropanol or dimethylaminoethoxyethanol, form stable intermediate byproducts that do not readily react with the promoter.
A degradation model for PZ-promoted MDEA that can be used for process design calculations using acidified solvent degradation to model the initial degradation rate over a range of CO2 loading and initial amine concentration was developed. Thermal degradation was modeled using second-order kinetics as a function of free amine and protonated amine. The degradation kinetics, along with the observed degradation products, suggest that the dominant pathway is by free PZ attack on a methyl substituent group of protonated MDEA to form diethanolamine (DEA) and 1-methylpiperazine (1-MPZ). The model predicts total amine loss from experimental CO2 degradation rate measurements within 20%. The modeling work was extended to other PZ-promoted tertiary amine solvents with bulkier substituent groups. PZ attack on ethyl or hydroxyethyl groups was 17% and 4% as fast, respectively, as attack on methyl groups.