Theses Doctoral

A study of catalytic metals and alkaline metal oxides leading to the development of a stable Ru-doped Ni Dual Function Material for CO2 capture from flue gas and in-situ catalytic conversion to methane

Arellano Treviño, Martha Alejandra

Atmospheric CO2 concentrations are at their highest level on record. Scientific evidence has demonstrated a direct correlation between the rise of CO2 levels and an increase of the global median temperature (~1°C higher than compared to the pre-industrial revolution times) due to the greenhouse gas effect. The change in climate due to this rapid increase of CO2 levels is already negatively affecting our ecosystem and lives, with unpredictable consequences in the future.

The main source of anthropogenic CO2 emissions is attributed to the combustion of fossil fuels for energy production and transportation. Global indicators signal that carbon-intensive fuels will continue to be utilized as a main energy source despite the rising implementation of renewable energy sources. In order to curb CO2 emissions, several carbon dioxide capture, utilization and sequestration (CCUS) technologies have been suggested. The current state-of-the-art CO2 capture technology utilizes toxic and corrosive aqueous amine solutions that capture CO2 at room temperature but require heating above the water boiling point temperatures to separate CO2 from the amine solution; the latter of which is to be recycled. Once the CO2 is purified, it is necessary to transport it to its sequestration site or an upgrading processing plant. These are complicated schemes that involve many energy-intensive and costly processes.

To address the shortcomings of these technologies, we propose a Dual Function Material (DFM) that both captures CO2 and catalytically converts it to methane in-situ. The DFM consists of a catalytic metal intimately in contact with an alkaline metal oxide supported on a high surface area carrier. The process operates within the flue gas at 320°C for both CO2 capture and methane generation upon the addition of renewable H2. The catalyst is required to methanate the adsorbed CO2 after the capture step is carried out in an O2 and steam-containing flue gas. Ruthenium, rhodium, and nickel are known CO2 methanation catalysts, provided they are in the reduced state. All three were compared for performance under DFM flue gas conditions. Ni is a preferred methanation catalyst based on price and activity; however, its inability to be reduced to its active state after experiencing O2-containing flue gas during the capture step was an outcome determined in this thesis. The performance of a variety of alkaline adsorbents (“Na2O”, CaO, “K2O” and MgO) and carriers (Al2O3, CeO2, CeO2/ZrO2 (CZO), Na-Zeolite-X (Na-X-Z), H-Mordenite Zeolite (H-M-Z), SiC, SiO2 and ZrO2-Y) were also studied. Selection of the best materials was based on CO2 capture capacity, net methane production and hydrogenation rates that were evaluated with thermogravimetric analysis and in fixed bed reactor tests.

Rh and Ru DFMs were effective methanation catalysts with Ru being superior based on capture capacity, hydrogenation rate and price. Ru remained active towards methanation even after exposure to O2 and steam-containing simulated flue gas. Alkaline adsorbents, in combination with reduced Ru, were tested for adsorption and methanation. Ru – “Na2O”/Al2O3 DFMs showed the highest rates for methanation although CaO is also a reasonable candidate with slightly lower methanation kinetics. To date, we have demonstrated that -Al2O3 is the most suitable carrier for DFM application relative to other materials studied.

The Ni-containing DFM, pre-reduced at 650°C, was highly active for CO2 methanation. However, the hydrogenation with 15% H2/N2 is completely inactive after exposure to O2 and steam, in a flue gas simulation, during the CO2 capture step at 320oC. This thesis reports that small amounts of precious metal (≤ 1% Pt, Pd or Ru) enhance the reduction (at 320°C) and activation of Ni-containing DFM towards methanation even after O2 exposure in a flue gas. While ruthenium is most effective, Pt and Pd all enhance reduction of oxidized Ni.

Another objective of this thesis was to investigate whether a portion of the Ru, at its current loading of 5%, could be replaced with less expensive Ni while maintaining its performance. The findings show that the main advantage of the presence of Ni is a small increase in CO2 adsorption and increase in methane produced, at the expense of a lower methanation rate. Extended cyclic aging studies corroborate the stable performance of 1% Ru, 10% Ni, 6.1% “Na2O”/Al2O3.

Characterization methods were used to monitor physical and chemical changes that may have occurred during aging studies. Measurements of the BET surface area, H2 chemisorption, XRD pattern, TEM images and STEM-EDS mapping were utilized to study and compare the structural and chemical changes between fresh and aged Ru doped Ni DFM samples. While similar BET surface areas were observed for the fresh and aged samples, some redispersion of the Ru and Ni sites was confirmed via H2 uptake and the observed decreases in Ru and Ni cluster size in the aged sample in comparison to the fresh. XRD patterns confirm an almost complete disappearance of the NiOx and RuOx species and the appearance of catalytically active Ru0 and Ni0 peaks on the aged sample compared to the fresh one. Further details of these methods, findings and conclusions are described in this thesis.


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More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
Farrauto, Robert
Ph.D., Columbia University
Published Here
November 11, 2019