Hailee Cox Christopher Dade Jessica Metter Cleaning up by getting dirty: Novel metal ion sourcing in CO2 Capture and Sequestration Hailee Cox Christopher Dade Jessica Metter

Purpose Atmospheric CO2 concentrations are at record levels; causing increasing global temperatures Coal-powered energy demand is on the rise globally and is a significant source of CO2 pollution A major reduction in atmospheric CO2 can be achieved by preventing it’s release into the air Current capture and sequestration systems fail to see the forest from the trees in terms of impact Concurrently, rising demand for fresh water is straining costal environments Is there a way both problems can be addressed simultaneously? Kang, D.; Lee, M.-G.; Jo, H.; Yoo, Y.; Lee, S.-Y.; Park, J. Carbon Capture and Utilization Using Industrial Wastewater Under Ambient Conditions. Chemical Engineering Journal 2017, 308, 1073–1080.

Overview Initial CO2 storage involved burying our problem in the sea Out of sight out of mind didn’t mean out of our environment CO2 readily reacts with aqueous metal ions to form stable salts that can be stored The First Question: how do you get CO2 into water? Amines The Second Question: Where are those metal salts coming from? Traditionally: Mines New EXCITING source: Wastewater It’s not just our thirst for energy that’s harming the environment Kang, D.; Lee, M.-G.; Jo, H.; Yoo, Y.; Lee, S.-Y.; Park, J. Carbon Capture and Utilization Using Industrial Wastewater Under Ambient Conditions. Chemical Engineering Journal 2017, 308, 1073–1080.

Structure and synthesis of DEA

DEA: good for more than policing people Diethanolamine (DEA) Secondary Amine Commercially useful Also a CO2 absorbent Binds CO2 in the air; transfers into aqueous phase for sequestration Kang, D.; Lee, M.-G.; Jo, H.; Yoo, Y.; Lee, S.-Y.; Park, J. Carbon Capture and Utilization Using Industrial Wastewater Under Ambient Conditions. Chemical Engineering Journal 2017, 308, 1073–1080. Healthline Media. Cancer-Causing Chemical Found in 98 Shampoos and Soaps. http://www.healthline.com/health-news/cancer-dangerous-chemical-found-in-shampoos-and-soaps-082913#1. (Accessed March 2017.)

DEA Synthesis: A star is born Yar, M.; Mushtaq, N.; Afzal, S. Synthesis, Reactions, Applications, and Biological Activity of Diethanolamine and Its Derivatives. Russian Journal of Organic Chemistry, 2013, 49 (7), 949-967.

DEA NMR Spec. H-NMR Unexpected number of signals Strong deshielding indicated C-NMR Highly symmetric molecule Some deshielding Yar, M.; Mushtaq, N.; Afzal, S. Synthesis, Reactions, Applications, and Biological Activity of Diethanolamine and Its Derivatives. Russian Journal of Organic Chemistry, 2013, 49 (7), 949-967.

Mechanism and performance

The Nitty Gritty Zwitterion mechanism of the CO2/DEA reaction and the formation of CaCO3 Miura, Y. Formations of Calcium-Carbonates by Natural and Artificial Shock Wave Impacts: New Type Formation of Carbonates. Lunar and Planetary Science, 2007, XXXVIII http://www.lpi.usra.edu/meetings/lpsc2007/pdf/1277.pdf (accessed March 7, 2017). Yar, M.; Mushtaq, N.; Afzal, S. Synthesis, Reactions, Applications, and Biological Activity of Diethanolamine and Its Derivatives. Russian Journal of Organic Chemistry, 2013, 49 (7), 949-967.

DEA CO2 Conversion Efficiency Kang, D.; Lee, M.-G.; Jo, H.; Yoo, Y.; Lee, S.-Y.; Park, J. Carbon Capture and Utilization Using Industrial Wastewater Under Ambient Conditions. Chemical Engineering Journal 2017, 308, 1073–1080.

Taking care of business Second proposed reaction mechanism exists Termolecular Other amines are better CO2 absorbers DEA is best CO2 converter because of it’s steric hindrance; ~50% conversion rate Stability of Zwitterion intermediate is key Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Code of Federal Regulations, Vol. 24, Table 302.4, 2004. Postnatal Development of Rat Pups After Maternal Exposure to Diethanolamine

It’s Gunna be ‘UUUGe! DEA is easily synthesized from commercial reagents Absorption capture methods are highly efficient Easy application to existing power plants Combines solutions to 2 growing environmental problems Gives scientists new avenues to connect climate research to everyday lives

NOT SO FAST… DEA is regulated by the EPA Potential amine release DEA exposure leads to life-long health consequences in certain mammals Significant energy is required to regenerate DEA catalysts Developing technology, Oxy-fuel Looping, holds the potential to replace absorbance technology DEA is regulated by the EPA - classified as a “hazardous air pollutant” under the Clean Air Act of 1990 and is listed as a “hazardous substance” by the Comprehensive Environmental Response, Compensation, and Liability Act Rats - dose of 0.1g/body mass/day caused negative impact - long half life Oxy-fuel in development but eliminates costly air separation (CO2 from Nitrogen) vs absorption Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA). Code of Federal Regulations, Vol. 24, Table 302.4, 2004. Postnatal Development of Rat Pups After Maternal Exposure to Diethanolamine Current Status Of Carbon Dioxide Capture And Storage Technologies. Renewable and Sustainable Energy Reviews 2014, 39, 426-443

Summary DEA strikes a balance between efficiency and energy costs An alternative to environmentally detrimental components has been successfully demonstrated Capture and sequestration system still has major limitations and downsides The next step forward on a path to truly sustainable and green society

Questions?