DEVELOPMENT OF ION EXCHANGE MODELS FOR WATER TREATMENT AND APPLICATION TO THE INTERNATIONAL SPACE STATION WATER PROCESSOR

The International Space Station (ISS) requires a substantial amount of potable water for use by the crew. The economic and logistic limitations of transporting the vast amount of water required onboard the ISS necessitate onboard recovery and reuse of the aqueous waste streams. Various treatment technologies are employed within the ISS water processor to render the waste water potable, including filtration, ion exchange, adsorption, and catalytic wet oxidation. The ion exchange resins and adsorption media are combined in multifiltration beds for removal of ionic and organic compounds. A mathematical model (MFBMODEL™) designed to predict the performance of a multifiltration (MF) bed was developed. MFBMODEL consists of ion exchange models for describing the behavior of the different resin types in a MF bed (e.g., mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins) and an adsorption model capable of predicting the performance of the adsorbents in a MF bed. Multicomponent ion exchange ii equilibrium models that incorporate the water formation reaction, electroneutrality condition, and degree of ionization of weak acids and bases for mixed bed, strong acid cation, strong base anion, and weak base anion exchange resins were developed and verified. The equilibrium models developed use a tanks-inseries approach that allows for consideration of variable influent concentrations. The adsorption modeling approach was developed in related studies and application within the MFBMODEL framework was demonstrated in the Appendix to this study. MFBMODEL consists of a graphical user interface programmed in Visual Basic and Fortran computational routines. This dissertation shows MF bed modeling results in which the model is verified for a surrogate of the ISS waste shower and handwash stream. In addition, a multicomponent ion exchange model that incorporates mass transfer effects was developed, which is capable of describing the performance of strong acid cation (SAC) and strong base anion (SBA) exchange resins, but not including reaction effects. This dissertation presents results showing the mass transfer model's capability to predict the performance of binary and multicomponent column data for SAC and SBA exchange resins. The ion exchange equilibrium and mass transfer models developed in this study are also applicable to terrestrial water treatment systems. They could be applied for removal of cations and anions from groundwater (e.g., hardness, nitrate, perchlorate) and from industrial process waters (e.g. boiler water, ultrapure water in the semiconductor industry).

DYNAMICS AND CONTROL OF REACTIVE DISTILLATION PROCESS FOR MONOMER SYNTHESIS OF POLYCARBONATE PLANTS

Polycarbonate (PC) is an important engineering thermoplastic that is currently produced in large industrial scale using bisphenol A and monomers such as phosgene. Since phosgene is highly toxic, a non-phosgene approach using diphenyl carbonate (DPC) as an alternative monomer, as developed by Asahi Corporation of Japan, is a significantly more environmentally friendly alternative. Other advantages include the use of CO2 instead of CO as raw material and the elimination of major waste water production. However, for the production of DPC to be economically viable, reactive-distillation units are needed to obtain the necessary yields by shifting the reaction-equilibrium to the desired products and separating the products at the point where the equilibrium reaction occurs. In the field of chemical reaction engineering, there are many reactions that are suffering from the low equilibrium constant. The main goal of this research is to determine the optimal process needed to shift the reactions by using appropriate control strategies of the reactive distillation system. An extensive dynamic mathematical model has been developed to help us investigate different control and processing strategies of the reactive distillation units to increase the production of DPC. The high-fidelity dynamic models include extensive thermodynamic and reaction-kinetics models while incorporating the necessary mass and energy balance of the various stages of the reactive distillation units. The study presented in this document shows the possibility of producing DPC via one reactive distillation instead of the conventional two-column, with a production rate of 16.75 tons/h corresponding to start reactants materials of 74.69 tons/h of Phenol and 35.75 tons/h of Dimethyl Carbonate. This represents a threefold increase over the projected production rate given in the literature based on a two-column configuration. In addition, the purity of the DPC produced could reach levels as high as 99.5% with the effective use of controls. These studies are based on simulation done using high-fidelity dynamic models.

THE POTENTIAL OF INDUSTRIAL WASTE AND AGRICULTURAL FEEDSTOCK TOWARDS SUSTAINABLE BIOFUELS PRODUCTION: TECHNO-ECONOMIC AND ENVIRONMENTAL IMPACT PERSPECTIVES

This Ph.D. research is comprised of three major components; (i) Characterization study to analyze the composition of defatted corn syrup (DCS) from a dry corn mill facility (ii) Hydrolysis experiments to optimize the production of fermentable sugars and amino acid platform using DCS and (iii) Sustainability analyses. Analyses of DCS included total solids, ash content, total protein, amino acids, inorganic elements, starch, total carbohydrates, lignin, organic acids, glycerol, and presence of functional groups. Total solids content was 37.4% (± 0.4%) by weight, and the mass balance closure was 101%. Total carbohydrates [27% (± 5%) wt.] comprised of starch (5.6%), soluble monomer carbohydrates (12%) and non-starch carbohydrates (10%). Hemicellulose components (structural and non-structural) were; xylan (6%), xylose (1%), mannan (1%), mannose (0.4%), arabinan (1%), arabinose (0.4%), galatactan (3%) and galactose (0.4%). Based on the measured physical and chemical components, bio-chemical conversion route and subsequent fermentation to value added products was identified as promising. DCS has potential to serve as an important fermentation feedstock for bio-based chemicals production. In the sugar hydrolysis experiments, reaction parameters such as acid concentration and retention time were analyzed to determine the optimal conditions to maximize monomer sugar yields while keeping the inhibitors at minimum. Total fermentable sugars produced can reach approximately 86% of theoretical yield when subjected to dilute acid pretreatment (DAP). DAP followed by subsequent enzymatic hydrolysis was most effective for 0 wt% acid hydrolysate samples and least efficient towards 1 and 2 wt% acid hydrolysate samples. The best hydrolysis scheme DCS from an industry's point of view is standalone 60 minutes dilute acid hydrolysis at 2 wt% acid concentration. The combined effect of hydrolysis reaction time, temperature and ratio of enzyme to substrate ratio to develop hydrolysis process that optimizes the production of amino acids in DCS were studied. Four key hydrolysis pathways were investigated for the production of amino acids using DCS. The first hydrolysis pathway is the amino acid analysis using DAP. The second pathway is DAP of DCS followed by protein hydrolysis using proteases [Trypsin, Pronase E (Streptomyces griseus) and Protex 6L]. The third hydrolysis pathway investigated a standalone experiment using proteases (Trypsin, Pronase E, Protex 6L, and Alcalase) on the DCS without any pretreatment. The final pathway investigated the use of Accellerase 1500® and Protex 6L to simultaneously produce fermentable sugars and amino acids over a 24 hour hydrolysis reaction time. The 3 key objectives of the techno-economic analysis component of this PhD research included; (i) Development of a process design for the production of both the sugar and amino acid platforms with DAP using DCS (ii) A preliminary cost analysis to estimate the initial capital cost and operating cost of this facility (iii) A greenhouse gas analysis to understand the environmental impact of this facility. Using Aspen Plus®, a conceptual process design has been constructed. Finally, both Aspen Plus Economic Analyzer® and Simapro® sofware were employed to conduct the cost analysis as well as the carbon footprint emissions of this process facility respectively. Another section of my PhD research work focused on the life cycle assessment (LCA) of commonly used dairy feeds in the U.S. Greenhouse gas (GHG) emissions analysis was conducted for cultivation, harvesting, and production of common dairy feeds used for the production of dairy milk in the U.S. The goal was to determine the carbon footprint [grams CO2 equivalents (gCO2e)/kg of dry feed] in the U.S. on a regional basis, identify key inputs, and make recommendations for emissions reduction. The final section of my Ph.D. research work was an LCA of a single dairy feed mill located in Michigan, USA. The primary goal was to conduct a preliminary assessment of dairy feed mill operations and ultimately determine the GHG emissions for 1 kilogram of milled dairy feed.

EVALUATING THE OIL SANDS RECLAMATION PROCESS: ASSESSING POLICY CAPACITY AND STAKEHOLDER ACCESS FOR GOVERNMENT AND NON-GOVERNMENTAL ORGANIZATIONS OPERATING IN ALBERTA’S OIL SANDS

By employing interpretive policy analysis this thesis aims to assess, measure, and explain policy capacity for government and non-government organizations involved in reclaiming Alberta's oil sands. Using this type of analysis to assess policy capacity is a novel approach for understanding reclamation policy; and therefore, this research will provide a unique contribution to the literature surrounding reclamation policy. The oil sands region in northeast Alberta, Canada is an area of interest for a few reasons; primarily because of the vast reserves of bitumen and the environmental cost associated with developing this resource. An increase in global oil demand has established incentive for industry to seek out and develop new reserves. Alberta's oil sands are one of the largest remaining reserves in the world, and there is significant interest in increasing production in this region. Furthermore, tensions in several oil exporting nations in the Middle East remain unresolved, and this has garnered additional support for a supply side solution to North American oil demands. This solution relies upon the development of reserves in both the United States and Canada. These compounding factors have contributed to the increased development in the oil sands of northeastern Alberta. Essentially, a rapid expansion of oil sands operations is ongoing, and is the source of significant disturbance across the region. This disturbance, and the promises of reclamation, is a source of contentious debates amongst stakeholders and continues to be highly visible in the media. If oil sands operations are to retain their social license to operate, it is critical that reclamation efforts be effective. One concern non-governmental organizations (NGOs) expressed criticizes the current monitoring and enforcement of regulatory programs in the oil sands. Alberta's NGOs have suggested the data made available to them originates from industrial sources, and is generally unchecked by government. In an effort to discern the overall status of reclamation in the oil sands this study explores several factors essential to policy capacity: work environment, training, employee attitudes, perceived capacity, policy tools, evidence based work, and networking. Data was collected through key informant interviews with senior policy professionals in government and non-government agencies in Alberta. The following are agencies of interest in this research: Canadian Association of Petroleum Producers (CAPP); Alberta Environment and Sustainable Resource Development (AESRD); Alberta Energy Regulator (AER); Cumulative Environmental Management Association (CEMA); Alberta Environment Monitoring, Evaluation, and Reporting Agency (AEMERA); Wood Buffalo Environmental Association (WBEA). The aim of this research is to explain how and why reclamation policy is conducted in Alberta's oil sands. This will illuminate government capacity, NGO capacity, and the interaction of these two agency typologies. In addition to answering research questions, another goal of this project is to show interpretive analysis of policy capacity can be used to measure and predict policy effectiveness. The oil sands of Alberta will be the focus of this project, however, future projects could focus on any government policy scenario utilizing evidence-based approaches.