Experimental study and kinetic model of monoethanolamine oxidative and thermal degradation for post-combustion CO 2 capture

Léonard, Grégoire; Toye, Dominique; Heyen, Georges

doi:10.1016/j.ijggc.2014.09.014

Cited by 39 publications

(56 citation statements)

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“…Owing to the complexity of the degradation kinetics, the exact reaction chemistry of oxidative degradation is not determined. Leonard et al adopted a methodology to propose an apparent reaction mechanism for oxidative degradation [26]. In the present work, the auto-catalytic reaction mechanism is developed on the same methodology.…”

Section: Auto-catalytic Mechanism and Kinetic Modelmentioning

confidence: 99%

“…Leonard et al adopted a methodology to propose an apparent reaction mechanism for oxidative degradation [26]. In the present work, the auto-catalytic reaction mechanism is developed on the same methodology.…”

Section: Auto-catalytic Kinetic Modelmentioning

confidence: 99%

“…The measurements from these pilot plants also point towards an existence of a correlation between dissolved metals and ammonia emissions. The reaction scheme of the proposed kinetic model is based on methodology suggested by Leonard et al [26]. Besides, to avoid the discrepancy between lab-scale degradation and amine oxidation during pilot scale PCCC, the kinetic parameters are based on regression of measurements from the EnBW pilot plant campaign.…”

Section: Introductionmentioning

confidence: 99%

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Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

et al. 2017

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Abstract:Oxidative degradation is a serious concern for upscaling of amine-based carbon capture technology. Different kinetic models have been proposed based on laboratory experiments, however the kinetic parameters included are limited to those relevant for a lab-scale system and not a capture plant. Besides, most of the models fail to recognize the catalytic effect of metals. The objective of this work is to develop a representative kinetic model based on an apparent auto-catalytic reaction mechanism between solvent degradation, corrosion and ammonia emissions. Measurements from four different pilot plants: (i) EnBW's plant at Heilbronn, Germany (ii) TNO's plant at Maasvlakte, The Netherlands; (iii) CSIRO's plants at Loy Yang and Tarong, Australia and (iv) DONG Energy's plant at Esbjerg, Denmark are utilized to propose a degradation kinetic model for 30 wt % ethanolamine (MEA) as the capture solvent. The kinetic parameters of the model were regressed based on the pilot plant campaign at EnBW. The kinetic model was validated by comparing it with the measurements at the remaining pilot campaigns. The model predicted the trends of ammonia emissions and metal concentration within the same order of magnitude. This study provides a methodology to establish a quantitative approach for predicting the onset of unacceptable degradation levels which can be further used to devise counter-measure strategies such as reclaiming and metal removal.

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Section: Auto-catalytic Mechanism and Kinetic Modelmentioning

confidence: 99%

Section: Auto-catalytic Kinetic Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

et al. 2017

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“…At the same time, the degradation rate was strongly accelerated (20% degradation over 7 days in oxidative conditions and 37% degradation over 3 weeks in thermal conditions) compared to the degradation rate reported in pilot plants (4% degradation over 45 days 8 ). As a consequence, the experimental equipment allowed for a detailed study of MEA thermal and oxidative degradation within reasonable time ranges 9 . In these studies, only pure MEA solutions were tested, and the presence of dissolved metals or additives in the solution has been neglected in first approach.…”

Section: General Contextmentioning

confidence: 99%

“…Two experiments are conducted in the absence of inhibitors, respectively with and without the metal mix described in the previous The conditions and the relevance of the base case experiment for the accelerated study of MEA oxidative degradation have been discussed in previous works 7,9 . However, the identified base NmL/min gas feed, 5% O 2 /15% CO 2 /80% N 2 , 1 week).…”

Section: Oxidative Degradationmentioning

confidence: 99%

Influence of Dissolved Metals and Oxidative Degradation Inhibitors on the Oxidative and Thermal Degradation of Monoethanolamine in Postcombustion CO₂ Capture

Léonard

Voice

Toye

et al. 2014

Ind. Eng. Chem. Res.

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In the present work, the influence of metal ions and oxidative degradation inhibitors on the stability of monoethanolamine solvents (MEA) is studied. 2 induces additional costs and impacts the environmental balance of the CO 2 capture process as well as its efficiency. The two main degradation pathways of MEA are studied under accelerated conditions: oxidative degradation with continuous gas feed and thermal degradation in batch reactors. It is confirmed that metal ions (resulting from solvent impurities and wall leaching) enhance the oxidative degradation of MEA, while they do not impact its thermal degradation.Moreover, different oxidative degradation inhibitors are tested with varying results according to the inhibitor. It appears that at the selected concentration, radical scavengers like Inhibitor A and DMTD (2,5-dimercapto-1,3,4-thiadiazole) are more efficient than chelating agents like HEDP(1-hydroxyethylidene diphosphonic acid) at inhibiting oxidative degradation. Furthermore, attention must be paid to the influence of oxidative degradation inhibitors on the thermal degradation of MEA. Indeed, some inhibitors like DMTD, DTPA (diethylenetriaminepentaacetic acid) and DTDP (3,3′-Dithiodipropionic acid) appeared to decrease the MEA thermal stability, which cannot be accepted in industrial applications. Finally, a further drawback of DTPA is its high affinity for metal ions leading to a more corrosive solution, so that its use is not recommended for CO 2 capture applications.

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Relevance of accelerated conditions for the study of monoethanolamine degradation in post‐combustion CO₂ capture

2014

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Solvent degradation represents one of the main operational drawbacks of the post-combustion CO 2 capture process. Degradation not only induces additional costs for solvent make-up, it also impacts the process efficiency and its environmental penalty due to the emission of various degradation products. There is still a gap of knowledge about the influence of process operating conditions on degradation, making it currently impossible to predict the solvent degradation rate in CO 2 capture plants. Morever, the reaction mechanisms corresponding to solvent degradation are very slow, significantly complicating its study in industrial units. In the present work, appropriate experimental equipment and analytical methods are developed for accelerating the degradation of monoethanolamine solvents (MEA). The relevance of accelerated conditions is established by comparing artificially degraded solvent samples with degraded solvent samples from industrial CO 2 capture pilot plants. Two approaches are evaluated implying either discontinuous or continuous gas feed, this latest being the most representative of industrial degradation. The respective influences of the gas feed composition and the gas-liquid transfer are evidenced and quantified. Finally, the present study leads to a better understanding of solvent degradation in the CO 2 capture process with MEA. More generally, it also evidences that accelerated conditions at laboratory-scale may provide relevant information for the study of slow phenomena taking place in large-scale industrial processes. Further works include the development of a kinetic model for MEA solvent degradation and the extension of this methodology to other promising solvents in order to facilitate the operation and large-scale deployment of CO 2 capture.

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Experimental study and kinetic model of monoethanolamine oxidative and thermal degradation for post-combustion CO 2 capture

Cited by 39 publications

References 13 publications

Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

Influence of Dissolved Metals and Oxidative Degradation Inhibitors on the Oxidative and Thermal Degradation of Monoethanolamine in Postcombustion CO₂ Capture

Relevance of accelerated conditions for the study of monoethanolamine degradation in post‐combustion CO₂ capture

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Experimental study and kinetic model of monoethanolamine oxidative and thermal degradation for post-combustion CO 2 capture

Cited by 39 publications

References 13 publications

Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

Understanding and Modelling the Effect of Dissolved Metals on Solvent Degradation in Post Combustion CO2 Capture Based on Pilot Plant Experience

Influence of Dissolved Metals and Oxidative Degradation Inhibitors on the Oxidative and Thermal Degradation of Monoethanolamine in Postcombustion CO2 Capture

Relevance of accelerated conditions for the study of monoethanolamine degradation in post‐combustion CO2 capture

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Influence of Dissolved Metals and Oxidative Degradation Inhibitors on the Oxidative and Thermal Degradation of Monoethanolamine in Postcombustion CO₂ Capture

Relevance of accelerated conditions for the study of monoethanolamine degradation in post‐combustion CO₂ capture