Matching Items (3)
Filtering by
- All Subjects: Carbon Sequestration
- All Subjects: Bipyridine
- All Subjects: Capacity Planning
- Genre: Academic theses
- Creators: Escobedo, Adolfo
- 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 Storage (CCS) is a climate stabilization strategy that prevents CO2 emissions from entering the atmosphere. Despite its benefits, impactful CCS projects require large investments in infrastructure, which could deter governments from implementing this strategy. In this sense, the development of innovative tools to support large-scale cost-efficient CCS deployment decisions is critical for climate change mitigation. This thesis proposes an improved mathematical formulation for the scalable infrastructure model for CCS (SimCCS), whose main objective is to design a minimum-cost pipe network to capture, transport, and store a target amount of CO2. Model decisions include source, reservoir, and pipe selection, as well as CO2 amounts to capture, store, and transport. By studying the SimCCS optimal solution and the subjacent network topology, new valid inequalities (VI) are proposed to strengthen the existing mathematical formulation. These constraints seek to improve the quality of the linear relaxation solutions in the branch and bound algorithm used to solve SimCCS. Each VI is explained with its intuitive description, mathematical structure and examples of resulting improvements. Further, all VIs are validated by assessing the impact of their elimination from the new formulation. The validated new formulation solves the 72-nodes Alberta problem up to 7 times faster than the original model. The upgraded model reduces the computation time required to solve SimCCS in 72% of randomly generated test instances, solving SimCCS up to 200 times faster. These formulations can be tested and then applied to enhance variants of the SimCCS and general fixed-charge network flow problems. Finally, an experience from testing a Benders decomposition approach for SimCCS is discussed and future scope of probable efficient solution-methods is outlined.
ContributorsLobo, Loy Joseph (Author) / Sefair, Jorge A (Thesis advisor) / Escobedo, Adolfo (Committee member) / Kuby, Michael (Committee member) / Middleton, Richard (Committee member) / Arizona State University (Publisher)
Created2017
Description
To maintain long term success, a manufacturing company should be managed and operated under the guidance of properly designed capacity, production and logistics plans that are formulated in coordination with its manufacturing footprint, so that its managerial goals on both strategic and tactical levels can be fulfilled. In particular, sufficient flexibility and efficiency should be ensured so that future customer demand can be met at a profit. This dissertation is motivated by an automobile manufacturer's mid-term and long-term decision problems, but applies to any multi-plant, multi-product manufacturer with evolving product portfolios and significant fixed and variable production costs. Via introducing the concepts of effective capacity and product-specific flexibility, two mixed integer programming (MIP) models are proposed to help manufacturers shape their mid-term capacity plans and long-term product allocation plans. With fixed tooling flexibility, production and logistics considerations are integrated into a mid-term capacity planning model to develop well-informed and balanced tactical plans, which utilize various capacity adjustment options to coordinate production, inventory, and shipping schedules throughout the planning horizon so that overall operational and capacity adjustment costs are minimized. For long-term product allocation planning, strategic tooling configuration plans that empower the production of multi-generation products at minimal configuration and operational costs are established for all plants throughout the planning horizon considering product-specific commonality and compatibility. New product introductions and demand uncertainty over the planning horizon are incorporated. As a result, potential production sites for each product and corresponding process flexibility are determined. An efficient heuristic method is developed and shown to perform well in solution quality and computational requirements.
ContributorsYao, Xufeng (Author) / Askin, Ronald (Thesis advisor) / Sefair, Jorge (Thesis advisor) / Escobedo, Adolfo (Committee member) / Yan, Hao (Committee member) / Arizona State University (Publisher)
Created2021