Matching Items (4)
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- All Subjects: Carbon Sequestration
- All Subjects: Water-energy Nexus
- Creators: Chester, Mikhail
- Status: Published
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
Carbon capture and sequestration (CCS) is one of the important mitigation options for climate change. Numerous technologies to capture carbon dioxide (CO2) are in development but currently, capture using amines is the predominant technology. When the flue gas reacts with amines (Monoethanaloamine) the CO2 is absorbed into the solution and forms an intermediate product which then releases CO2 at higher temperature. The high temperature necessary to strip CO2 is provided by steam extracted from the powerplant thus reducing the net output of the powerplant by 25% to 35%. The reduction in electricity output for the same input of coal increases the emissions factor of Nitrogen Oxides, Mercury, Particulate matter, Ammonia, Volatile organic compounds for the same unit of electricity produced. The thesis questions if this tradeoff between CO2 and other emissions is beneficial or not. Three different methodologies, Life Cycle Assessment, Valuation models and cost benefit analysis are used to identify if there is a net benefit to the society on implementation of CCS to a Pulverized coal powerplant. These methodologies include the benefits due to reduction of CO2 and the disbenefits due to the increase of other emissions. The life cycle assessment using ecoindicator'99 methodology shows the CCS is not beneficial under Hierarchical and Egalitarian perspective. The valuation model shows that the inclusion of the other emissions reduces the benefit associated with CCS. For a lower CO2 price the valuation model shows that CCS is detrimental to the environment. The cost benefit analysis shows that a CO2 price of at least $80/tCO2 is required for the cost benefit ratio to be 1. The methodology integrates Montecarlo simulation to characterize the uncertainties associated with the valuation models.
ContributorsSekar, Ashok (Author) / Williams, Eric (Thesis advisor) / Chester, Mikhail (Thesis advisor) / Allenby, Braden (Committee member) / Arizona State University (Publisher)
Created2012
Description
ABSTRACT Water and energy resources are intrinsically linked, yet they are managed separately even in the water scarce America southwest. This study develops a spatially explicit model of water energy inter-dependencies in Arizona and assesses the potential for co beneficial conservation programs. The interdependent benefits of investments in 8 conservation strategies are assessed within the context of legislated renewable energy portfolio and energy efficiency standards. The co- benefits of conservation are found to be significant. Water conservation policies have the potential to reduce statewide electricity demand by 1.0 - 3.0 %, satisfying 3.3 -10 % of the state's mandated energy-efficiency-standard. Adoption of energy -efficiency measures and renewable generation portfolios can reduce non - agricultural water demand by 2.3 - 12 %. The conservation co- benefits are typically not included in conservation plans or benefit cost analyses. Many co-benefits offer negative costs of saved water and energy, indicating that these measures provide water and energy savings at no net cost. Because ranges of costs and savings for water energy conservation measures are somewhat uncertain, future studies should investigate the co-benefits of individual conservation strategies in detail. Although this study focuses on Arizona, the analysis can be extended elsewhere as renewable portfolio and energy efficiency standards become more common nationally and internationally.
ContributorsBartos, Matthew D. (Author) / Chester, Mikhail (Thesis director) / Mays, Larry (Committee member) / Barrett, The Honors College (Contributor)
Created2013-12
Description
The Water-Energy Nexus (WEN) is a concept that recognizes the interdependence of water and energy systems. The Phoenix metropolitan region (PMA) in Arizona has significant and potentially vulnerable WEN interactions. Future projections indicate that the population will increase and, with it, energy needs, while changes in future water demand are more uncertain. Climate change will also likely cause a reduction in surface water supply sources. Under these constraints, the expansion of renewable energy technology has the potential to benefit both water and energy systems and increase environmental sustainability by meeting future energy demands while lowering water use and CO2 emissions. However, the WEN synergies generated by renewables have not yet been thoroughly quantified, nor have the related costs been studied and compared to alternative options.Quantifying WEN intercations using numerical models is key to assessing renewable energy synergy. Despite recent advances, WEN models are still in their infancy, and research is needed to improve their accuracy and identify their limitations. Here, I highlight three research needs. First, most modeling efforts have been conducted for large-scale domains (e.g., states), while smaller scales, like metropolitan regions, have received less attention. Second, impacts of adopting different temporal (e.g., monthly, annual) and spatial (network granularity) resolutions on simulation accuracy have not been quantified. Third, the importance of simulating feedbacks between water and energy components has not been analyzed.
This dissertation fills these major research gaps by focusing on long-term water allocations and energy dispatch in the metropolitan region of Phoenix. An energy model is developed using the Low Emissions Analysis Platform (LEAP) platform and is subsequently coupled with a water management model based on the Water Evaluation and Planning (WEAP) platform. Analyses are conducted to quantify (1) the value of adopting coupled models instead of single models that are externally coupled, and (2) the accuracy of simulations based on different temporal resolutions of supply and demand and spatial granularity of the water and energy networks. The WEAP-LEAP integrated model is then employed under future climate scenarios to quantify the potential of renewable energy technologies to develop synergies between the PMA's water and energy systems.
ContributorsMounir, Adil (Author) / Mascaro, Giuseppe (Thesis advisor) / White, Dave (Committee member) / Garcia, Margaret (Committee member) / Xu, Tianfang (Committee member) / Chester, Mikhail (Committee member) / Arizona State University (Publisher)
Created2022