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- All Subjects: MOF
- All Subjects: Methane recovery
- Creators: Lind, Marylaura
- Creators: Ibrahim, Amr
- Creators: McIntyre, Sean
- Status: Published
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
Global warming resulted from greenhouse gases emission has received widespread attention. Meanwhile, it is required to explore renewable and environmentally friendly energy sources due to the severe pollution of the environment caused by fossil fuel combustion. In order to realize a substantial adsorption process to resolve the environmental issues, the development of new adsorbents with improved properties has become the most critical issue. This dissertation presents the work of four individual but related studies on systematic characterization and process simulations of novel adsorbents with superior adsorption properties.
A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.
Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.
A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.
A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.
Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.
A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.
A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
ContributorsXu, Mai (Author) / Deng, Shuguang (Thesis advisor) / Lind, Marylaura (Committee member) / Lin, Jerry Y.S. (Committee member) / Green, Matthew D. (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2020