Carbon dioxide (CO₂) capture and sequestration (CCS) at fossil-fueled power plants is a critical technology for CO₂ emissions mitigation during the transition to a sustainable energy system. Post-combustion amine scrubbing is a relatively mature CO₂ capture technology, but barriers to implementation include high capital costs and energy requirements that reduce net power output by 20-30%. Capture energy requirements are typically assumed constant, but work investigates whether flexibly operating amine scrubbing systems in response to electricity market conditions can add value to CO₂ capture facilities while maintaining environmental benefits. Two versatile optimization models have been created to study the electricity system implications of flexible CO₂ capture. One model assesses the value of flexible capture at a single facility in response to volatile electricity prices, while the other represents a full electricity system to study the ability of flexible capture to meet electricity demand and reliability (ancillary) service requirements. Price-responsive flexible CO₂ capture has limited value at market conditions that justify CO₂ capture investments. Solvent storage can add value for price arbitrage by allowing flexible operation without additional CO₂ emissions, but only with favorable capital costs. The primary advantage of flexible CO₂ capture is an increased ability to provide grid reliability services and improve grid resiliency at minimum and maximum electricity demand. Flexibility mitigates capacity shortages because capture energy requirements need not be replaced, and variable capture at low demand helps respond to intermittent renewable generation. / text

This dissertation develops three game-theoretic models in each of its three chapters to explore the strategic implications of transparency in the administrative state. Each model contains a similar set of three players: a political principal, an agent representing an agency or a bureaucrat, and an interested third party. The models consider the utility of transparency as a tool for mitigating regulatory capture, in which the third party influences the agent to serve its interest rather than the principal's. Chapter 1, "Transparency and Media Scrutiny in the Regulatory Process," models transparency as the volume of records that the media receives from the agent, which raises the likelihood of news alleging low costs to the interest group after the agent's proposal of lax regulation. Such reports cost these two players and may deter the group from capturing the agent. Among other things, the model describes costs due to distorted policy proposals and loss of information when greater transparency causes inaccurate reports to increase along with accurate ones. In Chapter 2, "Transparency and Power in Rulemaking," transparency is a requirement for the agent to disclose an item of information, such as his message from the regulated party or his signal about the cost of regulation. The agent can always disclose this information, but doing so may increase the principal's power to set regulation higher than he or the regulated party desires. A key result is that transparency is not necessary for the principal to know as much as the agent does but may discourage the generation of the message or signal. Chapter 3, "A Reverse Rationale for Reliance on Regulators," suggests that an agent can benefit a principal not by gathering information from an outsider that she cannot access, but by preventing her from obtaining or acting on this information. The agent benefits the principal when he induces additional effort in the outside party's information generation because he is more adversarial toward that party than she is. Mandatory disclosure of the agent's information is harmful because it effectively allows the outsider to communicate directly with the principal and provide lower quality information.

Today, and for the foreseeable future, coal and other fossil fuels will provide a major portion of the energy services demanded by both developed and developing countries around the word. In order to reduce the emissions of carbon dioxide associated with combustion of coal for electricity generation, a wide range of carbon capture technologies are being developed. This thesis models the oxyfuel carbon capture process for pulverized coal and presents performance and cost estimates of this system in comparison to other low-carbon fossil fuel generators. Detailed process models for oxygen production, flue gas treatment, and carbon dioxide purification have been developed along with the calculation strategies necessary to employ these components in alternative oxyfuel system configurations for different types of coal-fired power plants. These new oxyfuel process models have been implemented in the widely-used Integrated Environmental Control Model (IECM) to facilitate systematic comparisons with other low-carbon options employing fossil fuels. Assumptions about uncertainties in the performance characteristics of gas separation processes and flue gas duct sealing technology, as well as plant utilization and financing parameters, were found to produce a wide range of cost estimates for oxyfuel systems. In case studies of a new 500 MW power plant burning sub-bituminous Powder River Basin coal, the estimated levelized cost of electricity (LCOE) 95% confidence interval (CI) was 86 to 150 [$/MWh] for an oxyfuel system producing a high-purity [99.5 mol% CO2] carbon dioxide product while capturing 90% of the flue gas carbon dioxide. For a CoCapture oxyfuel system capturing 100% of the flue gas CO2 together with all other flue gas constituents, the estimated LCOE 95% CI was 90 to 153 [$/MWh] (all costs in constant 2012 US Dollars). Using the IECM, an oxyfuel system for CO2 capture also was compared under uncertainty to an existing amine-based post-combustion capture system for a new 500 MW power plant, with both systems capturing 90% of the CO2 and producing a high-purity stream for pipeline transport to a geological sequestration site. The resulting distribution for the cost of CO2 avoided showed the oxyfuel-based system had a 95% CI of 44 to 126 [$/tonne CO2] while the amine-based system cost 95% CI ranged from 50 to 133 [$/tonne CO2]. The oxyfuel cost distribution had a longer tail toward more expensive configurations but over 70% of the distribution showed the oxyfuel-based system to be ~10[$/tonne CO2] lower in cost compared to the amine-based capture system. An evaluation of several low-carbon generation options fueled by coal and natural gas further considered both direct and indirect greenhouse gas emissions. This analysis showed oxyfuel to be economically competitive with all capture system considered, and also indicated oxyfuel to be the preferred carbon capture technology for minimizing overall carbon intensity. Combined, these results suggest that oxyfuel is a promising carbon capture technology, and the only one which offers the unique ability to capture all the combustion gases to become a truly zero emission coal plant. Realization of the latter option, however, is contingent on the development of new regulatory policies for underground injection of mixed flue gas streams that is outside the scope of this thesis.

In this thesis, I present four research papers related by their focus on environmental and economic effects of low-carbon policies and technologies in electric power. The papers address a number of issues related to the operation and design of CCS-equipped plants with solvent storage and bypass, the effect of Renewable Portfolio Standards (RPS) on cycling of coal-fired power plants, and the EPA’s proposed CO2 emissions rule for existing power plants. In Chapter 2, I present results from a study of the design and operation of power plants equipped with CCS with flue gas bypass and solvent storage. I considered whether flue gas bypass and solvent storage could be used to increase the profitability of plants with CCS. Using a pricetaker profit maximization model, I evaluated the increase in NPV at a pulverized coal (PC) plant with an amine-based capture system, a PC plant with an ammonia-based capture system, and a natural gas combined-cycle plant with an amine-based capture system when these plants were equipped with an optimally sized solvent storage vessel and regenerator. I found that while flue gas bypass and solvent storage increased profitability at low CO2 prices, they ceased to do so at CO2 prices high enough for the overall plant to become NPV-positive. In Chapter 3, I present results from a Unit Commitment and Economic Dispatch model of the PJM West power system. I quantify the increase in cycling of coal-fired power plants that results when complying with a 20% RPS using wind power, accounting for cycling costs not usually included in power plant bids. I find that while additional cycling does increase cycling-related production costs and emissions of CO2, SO2, and NOX, these increases are small compared to the overall reductions in production costs and air emissions that occur with high levels of wind. In proposing its existing power plant CO2 emissions standard, the Environmental Protection Agency determined that significant energy efficiency would be available to aid in compliance. In Chapter 4, I use an expanded version of the model of Chapter 3 to evaluate compliance with the standard with and without this energy efficiency, as well as under several other scenarios. I find that emissions of CO2, SO2, and NOX are relatively insensitive to the amount of energy efficiency available, but that production costs increase significantly when complying without efficiency. In complying with the EPA’s proposed existing power plant CO2 emissions standard, states will have the choice of whether to comply individually or in cooperation with other states, as well as the choice of whether to comply with a rate-based standard or a mass-based standard. In Chapter 5, I present results from a linear dispatch model of the power system in the continental U.S. I find that cooperative compliance reduces total costs, but that certain states will prefer not to cooperate. I also find that compliance with a mass-based standard increases electricity prices by a larger margin than does compliance with a rate-based standard, with implications for the distribution of surplus changes between producers and consumers.

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Progress towards the design and the application of small molecules as inhibitors of angiogenesis is reported. First, the regulation of hypoxia inducible transcription with epipolythiodioxopiperazine (ETP) natural products is discussed, beginning with the exploration of the physical and chemical properties of ETP skeletal analogs, xylylene-linked bis-diketopiperazines (1,4-piperazine-2,5-diones, DKPs).The design, synthesis and solid-state structures of a new class of xylylene-linked bis(1,4-piperazine-2,5-diones) are reported in an effort to extend the molecular framework of piperazine-2,5-diones. These compounds were derived from piperazine-2,5-dione as the core structure, synthesized via a new efficient route, and their crystal structures were determined. We examined the effects of side chain substitution on conformations of the linked bis-DKPs in the solid state. The results suggested that the interplay between the attractive intermolecular interactions and repulsive steric interactions of the substituents at the C6 and C6' positions of the diketopiperazine rings is important in determining the solid-state conformations of xylylene-linked bis(piperazine-2,5-diones).Asymmetric alpha-sulfenylation reactions were designed and performed as a potential route to the synthesis of epipolythiodioxopiperazine natural products. First, a chiral auxiliary approach is reported, sulfenylating chiral azomethines of alpha-amino acids as epipolythiodiketopiperazine precursors in yields of 55% with de as high as 74%. Asymmetric organocatalytic alpha-sulfenylation of substituted piperazine-2,5-diones is also reported, with chiral cinchona alkaloids as bases and benzyl-substituted electrophilic sulfur transfer reagents. The reaction was investigated with varied catalyst loading, type of sulfenylating agent, temperature and solvent. The effects of ring substitution and type of catalyst on yield and enantioselectivity of the reaction are reported. The synthetic utility of the asymmetric alpha-sulfenylation in context of the synthesis of epipolythiodioxopiperazine fungal metabolites is discussed.Finally, chemical approach towards the inhibition of angiogenesis by targeting alpha v beta 3 integrin antagonists with synthetic multifunctional boron neutron capture therapy (BNCT) integrin ligands is presented. The novel synthesis of an alpha v beta 3 integrin antagonist containing a free amine group for peripheral modification is reported, along with the preparation of a bifunctional BNCT integrin ligand and a trifunctional BNCT integrin ligand containing a fluorescent dye. Synthetic challenges and potential therapeutic applications of these ligands are discussed.

Carbon dioxide CO₂capture through hydrate formation is a novel technology under consideration as an efficient means of separating CO₂from flue/fuel gas mixtures for sequestration and enhanced oil recovery operations. This thesis examines post-combustion capture of CO₂from fossil-fuel power plant flue-gas streams through hydrate formation in a silica gel column. Power plant flue-gas contains essentially CO₂and nitrogen (N2) after suitable pre-treatment steps, thus a model flue-gas comprising 17% co₂and 83% N2 was used in the study. Previous studies employed a stirred-tank reactor to achieve water-gas contact for formation of hydrates; recent microscopic studies involved using water dispersed in silica gel to react with gas, showing potential for improved hydrate formation rates without the need for agitation. This study focuses on macroscopic kinetics of hydrate formation in silica gel to evaluate hydrate formation rates, CO₂separation efficiency and determining optimal silica gel properties as a basis for a CO2 capture process. Spherical silica gels with 30.0 and 100.0 nm pore sizes and 40-75 and 75-200 μm particle sizes were studied to determine pore size and particle size effects on hydrate formation. 100.0 nm pores achieved higher gas uptake and CO₂recovery over the 30.0 nm case. Improved CO₂separation was obtained when 75-200 μm particles with 100.0 nm pores were used. The two effects observed are due to improved gas diffusion occurring with larger pore and particle size, favouring increased hydrate formation. Compared to stirred-tank experiments, results in this study show a near four-fold increase in moles of gas incorporated in the hydrate per mole of water, showing that improved water-to-hydrate conversion is obtained with pore-dispersed water. At similar experimental conditions, CO₂recovery improved from 42% for stirred-tank studies to 51% for the optimum silica (100.0 nm 75-200 μm) determined in this study. Finally, effects of tetrahydrofuran (THF) - an additive that reduces operating pressure were evaluated. Experiments with 1 mol% THF, the optimum determined from previous stirred tank studies, showed improved gas consumption in silica but reduced CO₂recovery, indicating that the optimum concentration for use in silica is different from that in stirred-tank experiments.

A testing framework was developed to address system spatial and temporal performance characteristics in a two-dimensional (2D) human motion analysis system using commercially available digital video capture. The first testing protocol involved developing a method to evaluate system spatial performance characteristics with respect to accuracy, precision, and resolution. A physical model comprising a calibration frame was constructed with phantom postures selected to represent joint angles and off-plane movement typical of the activities of interest. This provided reference angles to which angles measured from digitally captured images were compared using the Bland and Altman method. Validation experiments confirmed that the principal sources of error were due to off-plane motion and pixel resolution in the video capture and analysis systems. In these analyses, it was verified that simulated experimental conditions could be corrected using the direct linear transform (DLT); however, the removal of parallax still resulted in 2 degrees of error in measured joint angles. The main source of error was resolution of the data acquisition system verified through Monte Carlo simulations. The second testing protocol involved developing a simple method to determine the temporal accuracy of motion analysis systems incorporating digital video cameras and a pendulum. A planar column pendulum with a natural frequency of 0.872 Hz was used to analyse five systems incorporating commercially available cameras and a single codec. The frame rate for each camera was measured to be within 3% of the US National Television Systems Committee (NTSC) broadcasting digital video standard of 29.97 fps.; however some cameras produced a frame duplication artefact. Least squares curve-fitting using a sinusoidal function revealed RMS differences between 3-5% for angular position and 5-15% for angular speed compared to the captured motion data. It was shown that some digital-video cameras and computer playback software contain data compression technology that may produce substantial temporal frame inaccuracies in recovered video sequences and that temporal accuracy should be evaluated in digital-based human motion analysis systems prior to their use in experimentation. / Thesis (Master, Mechanical and Materials Engineering) -- Queen's University, 2009-08-14 10:54:58.685

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