Theses Doctoral

A Study of Carbon Dioxide Capture and Catalytic Conversion to Methane using a Ruthenium, “Sodium Oxide” Dual Functional Material: Development, Performance and Characterizations

Wang, Shuoxun

The increasing CO2 level in the atmosphere, mostly attributed to anthropogenic activities, is overwhelmingly accepted to be the main greenhouse gas responsible for climate change. Combustion of fossil fuel is claimed to be the major cause of excess CO2 emission into the atmosphere, but human society will still rely heavily on fossil fuel for energy and feedstock supplements. In order to mitigate the environment-energy crisis and achieve a sustainable developing mode, Carbon Capture, Utilization and Storage (CCUS) is an effective method and attracts considerable interests.
Rather than conventional aqueous amine-based liquid absorbent, e.g. the toxic, corrosive and energy intensive monoethanolamine (MEA), solid adsorbents are preferable for CO2 capture. CO2 utilization via CO2 conversion to fuel or other value-added products is favored over CO2 storage. Also it is preferred that no transportation of captured CO2 is required. Capturing and converting CO2 to fuel, such as synthetic natural gas or CH4 is particularly useful if it is produced at the site of CO2 generation. The converted CO2 can then be recycled to the inlet of the power plant or integrated into existed fuel infrastructure eliminating any transportation.
This thesis presents a study of the development, performance and characterizations of a newly discovered (second generation) dual functional material (DFM) for CO2 capture and catalytic conversion to methane in two separated steps. This material consists of Ru as the methanation catalyst and “Na2O” obtained from Na2CO3 hydrogenation as the CO2 adsorbent, both of which are deposited on the high surface area γ-Al2O3 support. The Ru, “Na2O” DFM captures CO2 from O2- and steam-containing flue gas at temperature from 250 °C to 350 °C in step 1 and converts it to synthetic natural gas (CH4) at the same temperature with addition of H2 produced from excess renewable energy (solar and/or wind energy) in step 2. The heat generated from methanation drives adsorbed CO2 to Ru by spillover from the adsorption sites and diffuse to Ru for methanation. This approach utilizes the heat in the flue gas for both adsorption and methanation therefore eliminating the need of external energy input.
The second generation DFM was developed with a screening process of solid adsorbent candidates. Initial adsorption studies were conducted with powdered samples for CO2 capture capacity, methanation capability, and resistance to an O2-containing simulated flue gas feed. The new composition of DFM was then prepared with tablets for future industrial applications and scaled up to 10 grams suitable for testing in a fixed bed reactor. Parametric and 50-cycle aging studies were conducted in a newly constructed scaled-up fixed bed reactor using 10 grams of DFM tablets in the simulated flue gas atmosphere for CO2 capture.
With the presence of O2 in CO2 feed gas for step 1, the Ru catalyst is oxidized but must be rapidly reduced in step 2 to the active metallic state. Parametric studies identified 15% H2 is required for stable operation with no apparent deactivation. The parametric plus 50-cycle aging studies demonstrated excellent stability of the second generation DFM.
A kinetic study was also conducted for the methanation step using powdered DFM but prepared via the tablet method to minimize any mass transfer and diffusion influence on the methanation rate. An empirical rate law was developed with kinetic parameters calculated. The methanation rate of captured CO2 is highly dependent on H2 partial pressure (approaching a reaction order of 1) while essentially zero reaction order of CO2 coverage was determined. The kinetic study highlights the importance of H2 partial pressure on the methanation process.
Characterizations were conducted on the ground fresh and aged (underwent parametric and aging studies) DFM tablets. BET surface area, H2 chemisorption, X-ray diffraction (XRD) pattern, transmission electron microscopy (TEM) images and scanning transmission electron microscope- energy dispersive spectroscopy (STEM-EDS) mapping were utilized to study the material changes between fresh and aged samples. From fresh to aged, similar BET surface area was measured, improved both Ru and “Na2O” dispersion, and decreased Ru cluster size was observed while no definitive proof of the nature of the sodium species was obtained via XRD.
The second generation DFM containing 5% Ru, 6.1% “Na2O” / Al2O3 was shown to possess the capability of capturing CO2 from O2-containing simulated flue gas and subsequent methanation with addition of H2 produced from excess renewable energy (or from chemical processes) with twice the CO2 and CH4 capacity relative to the first generation DFM. Activity, selectivity and stability has been demonstrated for the second generation DFM.
We envision swing reactors to be utilized commercially where the flue gas feed for step 1 and H2 for step 2 are throttled alternatively between each reactor for continuous operation.


  • thumnail for Wang_columbia_0054D_14553.pdf Wang_columbia_0054D_14553.pdf application/pdf 4.97 MB Download File

More About This Work

Academic Units
Earth and Environmental Engineering
Thesis Advisors
Farrauto, Robert J.
Ph.D., Columbia University
Published Here
April 21, 2018