Abstract not available

<p> One of the major barriers to expanding the capacity of large-scale electrochemical energy storage within batteries is the threat of a catastrophic failure. Catastrophic battery pack failure can be initiated by a defect within a single battery cell. If the failure of a defective battery cell is not contained, the damage can spread and subsequently compromise the integrity of the entire battery back, as well as the safety of those in its surroundings. Replacing the volatile, flammable liquid electrolyte components found in most current lithium ion batteries with a solid polymer electrolyte (SPE) would significantly improve the cell-level safety of batteries; however, poor ionic conductivity and restricted operating temperatures compared to liquid electrolytes have plagued the practical application of SPEs. Rather than competing with the performance of liquid electrolytes directly, our approach to developing SPEs relies on increasing electrolyte functionality through the use of block copolymer architectures. </p><p> Block copolymers, wherein two or more chemically dissimilar polymer chains are covalently bound, have a propensity to microphase separate into nanoscale domains that have physical properties similar to those of each of the different polymer chains. For instance, the block copolymer, polystyrene-<i>b</i>-poly(ethylene oxide) (SEO), has often been employed as a solid polymer electrolyte because the nanoscale domains of polystyrene (PS) can provide mechanical reinforcement, while the poly(ethylene oxide) microphases can solvate and conduct lithium ions. Block copolymer electrolytes (BCEs) formed from SEO/salt mixtures result in a material with the bulk mechanical properties of a solid, but with the ion conducting properties of a viscoelastic fluid. The efficacy SEO-based BCEs has been demonstrated; the enhanced mechanical functionality provided by the PS domains resist the propagation of dendritic lithium structures during battery operation, thus enabling the use of a lithium metal anode. The increase in the specific energy of a battery upon replacing a graphite anode with lithium metal can offset the losses in performance due to the poor ion conduction of SPEs. However, BCEs that enable the use of a lithium anode and have improved performance would represent a major breakthrough for the development of high capacity batteries. </p><p> The electrochemical performance of BCEs has a complex relationship with the nature of the microphase separated domains, which is not well-understood. The objective of this dissertation is to provide fundamental insight into the nature of microphase separation and self-assembly of block copolymer electrolytes. Specifically, I will focus on how the ion-polymer interactions within a diverse set of BCEs dictate nanostructure. Combining such insight with knowledge of how nanostructure influences ion motion will enable the rational design of new BCEs with enhanced performance and functionality. </p><p> In order to facilitate the study of BCE nanostructure, synchrotron-based X-ray scattering techniques were used to study samples over a wide range of length-scales under conditions relevant to the battery environment. The development of the experimental aspects of the X-ray scattering techniques, as well as an improved treatment of scattering data, played a pivotal role in the success of this work. The dissemination of those developments will be the focus of the first section. </p><p> The thermodynamic impact of adding salt to a neutral diblock copolymer was studied in a model BCE composed of a low molecular weight SEO diblock copolymer mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), a common salt used in lithium batteries. In neutral block copolymers (BCPs), self-assembly is a thermodynamically driven process governed by a balance between unfavorable monomer contacts and the entropy of mixing. When the enthalpic and entropic contributions to free energy are similar in magnitude, a block copolymer can undergo a thermally reversible phase transition from an ordered to a disordered nanostructure. We used temperature-dependent small angle X-ray scattering (SAXS) to observe this transition in the model SEO/LiTFSI system. Unlike neutral BCPs, which to a first approximation are single component systems, the SEO/LiTFSI system demonstrated the thermodynamically stable coexistence phases of ordered lamellae and disordered polymer over a finite temperature window. Analysis of the lamellar domains revealed an increase in salt concentration during the ODT, indicating local salt partitioning due to the presence of nanostructure.</p><p> The performance of BCEs can also be improved by chemically functionalizing one of the polymer blocks by covalently attaching the salt anion. Since the cation is the only mobile species, these materials are coined single-ion conducting block copolymers. Single ion conduction can improve the efficiency of battery operation. In order for cation motion to occur in single-ion conducting block copolymers, it must dissociate from the backbone of the anion-containing polymer block. This direct coupling of ion dissociation (and hence conduction) and nanostructure has interesting implications for BCE performance. (Abstract shortened by ProQuest.) </p>

<p> Methane is the smallest hydrocarbon molecule, the fuel most widely studied in fundamental flame structure studies, and a major component of natural gas. Despite many decades of research into the fundamental chemical kinetics involved in methane oxidation, ongoing advancements in research suggest that more progress can be made. Though practical combustors of industrial and commercial significance operate at high pressures and turbulent flow conditions, fundamental understanding of combustion chemistry in flames is more readily obtained for low pressure and laminar flow conditions. </p><p> Measurements were performed from 1 to 0.1 atmospheres for premixed methane/air and non-premixed methane-nitrogen/oxygen flames in a counterflow. Comparative modeling with quasi-one-dimensional strained flame codes revealed bias-induced errors in measured velocities up to 8% at 0.1 atmospheres due to tracer particle phase velocity slip in the low density gas reacting flow. To address this, a numerically-assisted correction scheme consisting of direct simulation of the particle phase dynamics in counterflow was implemented. Addition of reactions describing the prompt dissociation of formyl radicals to an otherwise unmodified USC Mech II kinetic model was found to enhance computed flame reactivity and substantially improve the predictive capability of computed results for measurements at the lowest pressures studied. Yet, the same modifications lead to overprediction of flame data at 1 atmosphere where results from the unmodified USC Mech II kinetic mechanism agreed well with ambient pressure flame data. The apparent failure of a single kinetic model to capture pressure dependence in methane flames motivates continued skepticism regarding the current understanding of pressure dependence in kinetic models, even for the simplest fuels.</p>

<p>Lignocellulosic biomass is a renewable, sustainable resource that can replace or supplement fossil fuels use for liquid fuels and chemicals. However, its recalcitrant structure including interwoven cellulose, hemicelluloses, and lignin biomacromolecules is challenging to deconstruct. Pretreating biomass so that it can be converted to useful liquids dominates process economics. Many pretreatment methods exist, but most require hazardous chemicals or processing conditions. Many ionic liquids (ILs), salts molten below 100&deg;C, can be used to deconstruct lignocellulosic biomass and are less hazardous than the volatile organic compounds typically used. </p><p> While effective, relatively safe, and recyclable, ILs are expensive. To reduce costs, dilution with other safe compounds is desirable, if there is no impact on deconstruction efficiency. Glycerol, a food additive, is inexpensive and becoming even more so since it is a by-product of the burgeoning biodiesel industry. Use of glycerol as an additive or diluent for ILs is extensively evaluated in this work. </p><p> Rice hulls are an abundant biomass, with over 100 million tons produced per year, but with little practical use. The IL 1-ethyl-3-methylimidazolium formate ([C2mim][O2CH] or EMIM Form) when mixed with an equal amount of glycerol has been shown to be effective in pretreating rice hulls. Ambient pressure, a pretreatment temperature of 110&deg;C, and a reaction time of three hours produced rice hulls that could be enzymatically hydrolyzed to give reasonably good glucose and xylose yields considering the recalcitrance of this silica-armored biomass. </p><p> The IL [C2mim][O2CH] was also effective when mixed with an equal amount of glycerol to pretreat loblolly pine, a fast-growing softwood. Loblolly pine was pretreated at 140&deg;C for three hours to produce a solid rich in cellulose and hemicelluloses, while a lignin-rich product could be precipitated from the IL. Similar products were obtained from pretreatment with a mixture of 75% 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc] or EMIM Ac) and 25% glycerol. Enzymatic hydrolysis of the pretreated solids gave glucose, mannose, and xylose yields up to 18 times that of the raw pine. </p><p> Viscosity measurements of pure glycerol, [C2mim][O2CH], [C2mim][OAc], and IL-glycerol mixtures were very different at ambient temperature, but were similar at typical biomass pretreatment temperatures. Biomass pretreated by mixtures with higher viscosity tended to give better carbohydrate yields after enzymatic hydrolysis. Higher excess molar volumes, <i>V_m^E</i>, tended to align with better carbohydrate yields after enzymatic hydrolysis. This phenomenon may relate to more energy put into shearing flow of the IL-glycerol-biomass system resulting in biomass particle shearing or stretching that allowed better solvent access into the biomass. </p>

Thesis submitted in fulfilment of the requirements for the degree of Master of Technology: Chemical Engineering, In the Faculty of Engineering, Cape Peninsula University of Technology 2014 / Energy efficiency has become an important feature in the design of process plants due to the rising cost of energy and the more stringent environmental regulations being implemented worldwide. In South Africa as in other African countries, most of the chemical plants were built during the era of cheap energy with little emphasis placed on energy efficiency due to the abundance of cheap utility sources such as coal and crude oil. In most of these plants, there exists significant potential for substantial process heat recovery by conceptual integration of the plant’s heat exchangers. Pinch Technology (PT) has been demonstrated to be a simple and very effective technique for heat integration and process optimization. This study applies the PT approach to retrofit the heat exchangers network of the Crude Distillation Unit (CDU), of a complex petroleum refinery with the aim to reduce utilities requirement and the associated gaseous pollutants emission. This objective is accomplished by firstly conducting an energy audit of the unit to scope for potential energy saving. The existing Heat Exchanger Network (HEN) was re-designed using the remaining problem analysis (RPA) to achieve improved process energy recovery while making maximum use of the existing exchangers. The aim is to maintain the existing plant topology as much as possible. This network was later relaxed trading heat recovery with number of heat transfer unit so as to optimize the capital cost. These were implemented in AspenPlus v7.2 environment. The cost implications of the retrofitted and evolved networks including the capital and operating costs were determined on a 5 years payback time basis. The Problem Table (PT) analysis revealed that the minimum utilities requirements are 75 MW and 55 MW for the hot and cold utilities respectively. Compared to the existing utilities requirements of 103 MW for hot utility and 83 MW for cold utility, this represent a potential savings of about 26 % and 33 % savings for the hot and cold utilities respectively. The target utilities usage in the re-designed network after applying Remaining Problem Analysis (RPA) was found to be 55 MW for the cold utility and 75 MW for hot utility. The relaxed HEN required a cold utility of 62.5 MW and hot utility of 81 MW. From the total cost estimation, it was found that, although an energy saving of 34% can be achieved by the re-designed network before relaxation, the capital cost, US$ 1670000 is significantly higher than for the existing network (about US$ 980000). The final relaxed network gave an energy saving of 34% and with total cost of US$ 1100000. It was recommended from the study after cost comparisons of the four different networks (the original network, the MER network, the relaxed network and a grass-root design) that the best network for the retrofit purpose was the relaxed HEN, because there is no major shift in deviation from the topology of the original network. From the analysis it was found that a 34% saving in energy cost could be achieved from this retrofit. The Total Annual Cost (TAC) for this network gives credence to the fact that this retrofit which applied the rules of pinch analysis can bring about real saving in energy usage.