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- Creators: Green, Matthew
- Creators: Ibrahim, Amr
Description
The large-scale anthropogenic emission of carbon dioxide into the atmosphere leads to many unintended consequences, from rising sea levels to ocean acidification. While a clean energy infrastructure is growing, mid-term strategies that are compatible with the current infrastructure should be developed. Carbon capture and storage in fossil-fuel power plants is one way to avoid our current gigaton-scale emission of carbon dioxide into the atmosphere. However, for this to be possible, separation techniques are necessary to remove the nitrogen from air before combustion or from the flue gas after combustion. Metal-organic frameworks (MOFs) are a relatively new class of porous material that show great promise for adsorptive separation processes. Here, potential mechanisms of O2/N2 separation and CO2/N2 separation are explored.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
First, a logical categorization of potential adsorptive separation mechanisms in MOFs is outlined by comparing existing data with previously studied materials. Size-selective adsorptive separation is investigated for both gas systems using molecular simulations. A correlation between size-selective equilibrium adsorptive separation capabilities and pore diameter is established in materials with complex pore distributions. A method of generating mobile extra-framework cations which drastically increase adsorptive selectivity toward nitrogen over oxygen via electrostatic interactions is explored through experiments and simulations. Finally, deposition of redox-active ferrocene molecules into systematically generated defects is shown to be an effective method of increasing selectivity towards oxygen.
ContributorsMcIntyre, Sean (Author) / Mu, Bin (Thesis advisor) / Green, Matthew (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2019
Description
Within recent years, metal-organic frameworks, or MOF’s, have gained a lot of attention in the materials research community. These micro-porous materials are constructed of a metal oxide core and organic linkers, and have a wide-variety of applications due to their extensive material characteristic possibilities. The focus of this study is the MOF-5 material, specifically its chemical stability in air. The MOF-5 material has a large pore size of 8 Å, and aperture sizes of 15 and 12 Å. The pore size, pore functionality, and physically stable structure makes MOF-5 a desirable material. MOF-5 holds applications in gas/liquid separation, catalysis, and gas storage. The main problem with the MOF-5 material, however, is its instability in atmospheric air. This inherent instability is due to the water in air binding to the zinc-oxide core, effectively changing the material and its structure. Because of this material weakness, the MOF-5 material is difficult to be utilized in industrial applications. Through the research efforts proposed by this study, the stability of the MOF-5 powder and membrane were studied. MOF-5 powder and a MOF-5 membrane were synthesized and characterized using XRD analysis. In an attempt to improve the stability of MOF-5 in air, methyl groups were added to the organic linker in order to hinder the interaction of water with the Zn4O core. This was done by replacing the terepthalic acid organic linker with 2,5-dimethyl terephthalic acid in the powder and membrane synthesis steps. The methyl-modified MOF-5 powder was found to be stable after several days of exposure to air while the MOF-5 powder exhibited significant crystalline change. The methyl-modified membrane was found to be unstable when synthesized using the same procedure as the MOF-5 membrane.
ContributorsAnderson, Anthony David (Author) / Lin, Jerry Y.S. (Thesis director) / Ibrahim, Amr (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Carbon capture is an essential way to reduce greenhouse gas emissions. One way to decrease the emissions is through the use of adsorbents such as zeolites. Dr. Dong-Kyun Seo’s group (School of Molecular Sciences, Arizona State University) synthesized the nanostructured faujasite (NaX). The zeolite was characterized using Scanning Electron Microscopy (SEM) and the physisorption properties were determined using ASAP 2020. ASAP 2020 tests of the nano-zeolite pellets at 77K in a liquid N2 bath determined the BET surface area of 547.1 m2/mol, T-plot micropore volume of 0.2257 cm3/g, and an adsorption average pore width of 5.9 Å. The adsorption isotherm (equilibrium) of CH4, N2, and CO2 were measured at 25ºC. Adsorption isotherm experiments concluded that the linear isotherm was the best fit for N2, and CH4 and the Sips isotherm was a better fit than the Langmuir and Freundlich isotherm for CO2. At 25ºC and 1 atm the zeolite capacity for CO2 is 4.3339 mmol/g, 0.1948 mmol/g for CH4, and 0.3534 mmol/g for N2. The zeolite has a higher CO2 capacity than the conventional NaX zeolite. Breakthrough experiments were performed in a fixed bed 22in, 0.5 in packing height and width at 1 atm and 298 K with nano-zeolite pellets. The gas chromatographer tested and recorded the data every two minutes with a flow rate of 10 cm3/min for N2 and 10 cm3/min CO2. Breakthrough simulations of the zeolite in a fixed bed adsorber column were conducted on MATLAB utilizing varying pressures, flow rates, and fed ratios of various CO2, N2 and CH4. Simulations using ideal adsorbed solution theory (IAST) calculations determined that the selectivity of CO2 in flue gas (15% CO2 + 85% N2) is 571.79 at 1 MPa, significantly higher than commercial zeolites and literature. The nanostructured faujasite zeolite appears to be a very promising adsorbent for CO2/N2 capture from flue gas and the separation of CO2/N2.
ContributorsClark, Krysta D. (Author) / Deng, Shuguang (Thesis director) / Green, Matthew (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
The cost of capturing carbon dioxide (CO2) from ambient air needs to be greatly reduced if it is to contribute significantly to mitigating climate change. Ion-exchange resin (IER) with quaternary ammonium cation binds CO2 when dry and releases it when wet without supplemental energy, making the process attractive for economical Direct Air Capture (DAC). In this study, a design case basis was developed for a system of collectors capable of capturing 1000 tons/day of CO2 via moisture swing sorption. The model uses varying weather parameters such as temperature, wind speed, and relative humidity to understand the impact of weather on the sorbent loading, cycle time (capture and regeneration), and net water loss. Two independent isotherm models, namely Flory Huggins and the modified Langmuir isotherm model were used to estimate the water and CO2 loading of the resin respectively as a function of relative humidity. The capture model suggests a higher capture rate during the summer and daytime (in a diurnal cycle) as the relative humidity is lower. A design optimization model was developed to minimize the capture time and maximize the sorbent loading. The crude rate production and the net water loss can help conduct an economic analysis to determine the cost of carbon capture.
ContributorsTalha, Mohammad Abu (Author) / Green, Matthew (Thesis advisor) / Lackner, Klaus (Committee member) / Cirucci, John (Committee member) / Arizona State University (Publisher)
Created2023