Sponsored by IONICON AnalytikReviewed by Andrea SalazarDec 9 2024
In the process of Carbon Capture and Storage (CCS), carbon dioxide (CO2) is chemically absorbed through amine solutions. Proton Transfer Reaction-Time of Flight Mass Spectrometry (PTR-TOF) analyzers can monitor amine emissions and degradation products in real time.
Image Credit: TCM
CCS technologies are a critical element in reducing CO2 emissions to combat global warming.
When it comes to CCS techniques, amine-based post-combustion CO2 capture is the oldest technology. Using amine solvents to scrub CO2 from flue gases can lead to the release of amine emissions and their degradation products into the atmosphere, which presents both health and environmental risks.
Accurately monitoring this type of emission is crucial in ensuring compliance with environmental regulations and optimizing CCS processes.
PTR-TOF is a significant ally in the sensitive, real-time monitoring of amine emissions in CCS applications. This document details using PTR-TOF analyzers for monitoring minuscule amine levels and their degradation products in ambient air and flue gases, as well as the benefits of utilizing this technology in industrial environments that are demanding.
Background on Amine-Based CO2 Capture
In amine-based CCS, CO2 is chemically absorbed through aqueous amine solutions, like monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP) or piperazine (PZ), all of which form soluble salts with CO2.
The salts regenerate, releasing pure CO2 for storage. Although effective, this process creates amine emissions and degradation products, including aldehydes, ammonia, and nitrosamines, which require careful monitoring to reduce environmental and health risks.1,2
PTR-TOF - The Ideal Monitoring Tool
PTR-TOF is a highly sensitive analytical technique that allows for the real-time detection of volatile organic compounds such as amines. Molecules are ionized through proton transfer from H3O ions, which enables the non-destructive analysis of gas-phase compounds at minuscule levels.3,4
Since being introduced in the mid-90s, PTR-TOF has seen extensive application in a wide array of scientific research fields.
For a number of years, PTR-TOF gained acceptance for industrial applications. In particular, the semiconductor industry is well known to have very rigid monitoring requirements and is now established as a technology with all leading manufacturers.
This proven history highlights the reliability and robustness of IONICON PTR-TOF systems for industrial applications that are demanding, including CCS.5
Key Features of PTR-TOF for CCS Applications: High Sensitivity: PTR-TOF is capable of detecting amines and degradation products at concentrations as low as parts per trillion (ppt). This is crucial when monitoring emissions from large-scale CCS facilities.6 Real-time Monitoring: In contrast to conventional methods that need offline sampling and analysis, PTR-TOF offers continuous, real-time data with high temporal resolution, giving operators the opportunity to respond quickly to emission level fluctuations.3 Versatility: PTR-TOF is capable of detecting a wide array of organic compounds, such as amines, aldehydes, ammonia, nitrosamines, and other Hazardous Air Pollutants (HAPs) like acetonitrile or acetamide, as well as other typical degradation products like pyrazines or pyrroles, making it ideal for monitoring complex samples often encountered in CCS processes.7,8 Unparalleled performance: The IONICON PTR-TOF analyzer uniquely integrates three features: high mass resolution, pure H3O+ ion chemistry, and low field-induced fragmentation. This makes it an exceptional instrument for analyzing highly complex samples, such as amine-treated flue gas. Compact and Industrial-Grade: Industrial types of PTR-TOF are compact and built to be integrated into standard racks or industrial analyzer cabinets. Their reliability and robustness make them well-suited for long-term deployment in industrial settings. These instruments are masters of the challenges found in many demanding industrial applications where real-time emission monitoring is essential.5,9
Example of a 19" PTR-TOF system that can easily be integrated into cabinets or be used as stand-alone units. Image Credit: IONICON Analytik
Case Study: Emission Monitoring at Technology Centre Mongstad
PTR-TOF has seen successful use at the Technology Centre Mongstad (TCM) for over ten years. The emission monitoring campaigns performed at TCM, which use PTR-TOF, have shown the ability of the instrument to continuously track amine emissions at sub-ppb levels.
A recent study demonstrated that the instrument monitored MEA and degradation products like ammonia and nitrosamines and detected them at levels far below regulatory limits.6 The advanced sampling setup, which included a heated extraction probe and sampling lines, allowed for accurate real-time measurements.
Updates at GHGT-17
A summary of the activities and most recent results of amine and amine degradation product monitoring through the use of PTR-TOF was presented at the GHGT-17 Conference by IONICON's partner company, Advanced Monitoring Solutions (adMS).5
Professor Armin Wisthaler's presentation, entitled "An Update on Emission Monitoring of Amines and Amine Degradation Products by PTR-ToF-MS," showcases the continual improvement in PTR-TOF technology when it comes to emission monitoring.
Included in these advancements are improvements to the detection limits for trace amines and nitrosamines, as well as integrating real-time emission data into plant management systems.
An example of this data is shown below. By displaying emission data in real-time to plant operators, it became feasible to ensure continuous monitoring and quick decision-making. This real-time ability improves process control and allows the plant to keep within rigid emission limits.
Display of emission data in real-time. Image Credit: IONICON Analytik
Conclusion
This study shows that PTR-TOF is a reliable and versatile tool for monitoring amine emissions in CCS applications. The ability to offer real-time, highly sensitive detection of a wide array of compounds makes it irreplaceable in ensuring environmental compliance and optimizing process efficiency.
As PTR-TOF technology keeps evolving, it will have an increasingly crucial role in the large-scale utilization of CCS technologies around the world.
Technology Centre Mongstad (TCM) is the world's largest plant for testing and improving technologies for CO2 capture. Image Credit: TCM
References and Further Reading Nielsen, C. J., et al. Atmospheric Degradation of Amines (ADA) Summary Report: Photo-Oxidation of Methylamine, Dimethylamine and Trimethylamine CLIMIT project no. 201604 Scientific report. Available at: https://nilu.com/wp-content/uploads/dnn/02-2011-mka-ADA-final-report.pdf. Klett, G. (2013). Carbon Capture and Storage. [online] Umweltbundesamt. Available at: https://www.umweltbundesamt.de/themen/wasser/gewaesser/grundwasser/nutzung-belastungen/carbon-capture-storage#grundlegende-informationen. Morken, A.K., et al. (2014). Emission Results of Amine Plant Operations from MEA Testing at the CO2 Technology Centre Mongstad. Energy Procedia, 63, pp.6023-6038. https://doi.org/10.1016/j.egypro.2014.11.636. Nielsen, C.J., et al (2012). Atmospheric Degradation of Amines (ADA). Summary report from atmospheric chemistry studies of amines,... [online] ResearchGate. unknown. Available at: https://www.researchgate.net/publication/255979042_Atmospheric_Degradation_of_Amines_ADA_Summary_report_from_atmospheric_chemistry_studies_of_amines_nitrosamines_nitramines_and_amides [Accessed 13 Nov. 2024]. Wikipedia Contributors (2019). Carbon capture and storage. [online] Wikipedia. Available at: https://en.wikipedia.org/wiki/Carbon_capture_and_storage. Learning Toolbox Viewer. Available at: https://my.ltb.io/www/#/ (Accessed 6 Dec. 2024). Wisthaler, A., Mikoviny, T. and Languille, B. (2022). Ultra-Sensitive Detection of Impurities In CO2. SSRN Electronic Journal. https://doi.org/10.2139/ssrn.4294576. Zhu, L., Mikoviny, T., et al. (2018). A compact and easy-to-use mass spectrometer for online monitoring of amines in the flue gas of a post-combustion carbon capture plant. International Journal of Greenhouse Gas Control, 78, pp.349-353. https://doi.org/10.1016/j.ijggc.2018.09.003.
This information has been sourced, reviewed and adapted from materials provided by IONICON Analytik.
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