1. 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

2. 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.

3. 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.

4. Structure and synthesis of DEA

5. 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. (Accessed March 2017.)

6. 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),

7. 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),

8. Mechanism and performance

9. 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 (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),

10. 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.

11. 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

12. 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

13. 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,

14. 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

15. Questions?