Graduation date: 1994

Thermochemical processes for hydrogen production driven by nuclear energy are promising alternatives to existing technologies for large-scale commercial production of hydrogen, without dependence on fossil fuels. In the Copper-Chlorine (Cu-Cl) cycle, water is decomposed in a sequence of intermediate processes with a net input of water and heat, while hydrogen and oxygen gases are generated as the products. The Super Critical Water-cooled Reactor (SCWR) has been identified as a promising source of heat for these processes. In this thesis, the process analysis and simulation models are developed using the Aspen PlusTM chemical process simulation package, based on experimental work conducted at the Argonne National Laboratory (ANL) and Atomic Energy of Canada Limited (AECL). A successful simulation is performed with an Electrolyte Non Random Two Liquid (ElecNRTL) model of Aspen Plus. The efficiency of the cycle based on three and four step process routes is examined in this thesis. The thermal efficiency of the four step thermochemical process is calculated as 45%, while the three step hybrid thermochemical cycle is 42%, based on the lower heating value (LHV) of hydrogen. Sensitivity analyses are performed to study the effects of various operating parameters on the efficiency, yield, and thermodynamic properties. Possible efficiency improvements are discussed. The results will assist the development of a lab-scale cycle which is currently being conducted at the University of Ontario Institute of Technology (UOIT), in collaboration with its partners. / UOIT

Disinfectants, such as chlorine, are widely used in water treatment plants to ensure the safety and quality of drinking water. However, these disinfectants easily react with some natural or man-made organic compounds in raw water and form disinfection by-products (DBPs). For example, halogenated acetic acid (HAAs) and trihalomethanes (THMs) are two main components of DBPs. These DBPs contained in drinking water will increase the risk of cancer in human body. Therefore, researches on halogenated acetic acid¡¦s potential of causing cancer have increased currently. Organic acids are usually the reactants which proceed in chlorination reaction into products of disinfection by-products in water treatment plant. The purpose of this study is to investigate adsorption characteristics in solution by using tests of kinetics and equilibrium adsorptions and kinetic model evaluations of selected fulvic acids (FA) extracted from raw water. Therefore, we use commercial single-walled carbon nanotube (SWCNT) for the adsorbents, and calculate thermodynamic parameters (£GG, £GS and £GH) in order to further understand the adsorption mechanism of CNTs. The maximum adsorbed amounts of FA onto SWCNTs was calculated by the Langmuir model at 25¢J, reaching 61.88mg / g which were much higher than that onto commercially available granular activated carbon (10.69 mg/g). The adsorption capacity of FA onto CNTs increased with decreasing outer diameter of CNTs (dp), molecular weight of FA, trmperature and pH value in all texts. In the condition of constant temperature 25¢J, we analyzed HAAFP after the test of equilibrium adsorption and that the removal efficiency of HAAFP could reach 40.76%. The best selection in kinetic models evaluation, fitting models such as Modified Freundlich equation, Pseudo-1st-order equation and Pesudo-2nd-oder equation, is Modified Freundlch equation model. In addition, intraparticle diffusion equation model was fitted well and showed adsorption process was controlled by pore diffusion. We calculated the activation energy of carbon nanotube adsorption of FA and found that film diffusion was the main factor for controlling reaction rate. According to results of thermodynamic parameters indicated that the adsorption was spontaneously and an exothermic reaction. It is obvious that the adsorption capacity as well as the reaction rate of CNTs are superior to that of granular activated carbon in raw water. These results suggest that CNTs possess highly potential applications in environmental protection. In the future, if we can combine nanotube technology with disinfection technology and apply such technique on the end of processing unit for design of either the domestic treatment facilities or small simple water treatment in drinking water. Thus it will enhance the new treatment technology of drinking water and the safety of the public health. Another possibility will be to promote the opportunity of marketing development in drinking water.

Chlorine is always used in disinfection process of water treatment plant (WTP) in Kaohsiung, and the major of disinfection by-products (DBPs) is THMs. Reaction of THMs producing were found in relation to lots of factors of water quality. Therefore we used SPSS to analysis the relation between water quality and THMs content for making prediction model of THMs formation in water distribution system in downtown Kaohsiung city. It is expected to estimate the concentration of THMs with a simple method, and to reduce THMs by controlling some items of water quality. While the variance of TOC value is low, we found that concentration of THMs is related to temperature, pH, and residual chlorine by regression method. In these items, residual chlorine had the highest correlation. While the variance of TOC value is high, the correlation between the three items and THMs is weaker than the front one. From this finding, TOC is best one fitting factor in prediction of THMs. In this study, we found that R-square value of Multivariate regression prediction is higher than the value of Univariate regression prediction probably for THMs producing is a complex reaction, so formation model was hard using only one item of water quality.

The main objective of this study was to conduct a systematic investigation of the disinfection by-products (DBPs) formation in low-bromide and low- specific ultraviolet absorbance (SUVA) waters and the control of DBP precursors by nanofiltration (NF) and ultrafiltration (UF) processes in such waters. To this end, firstly, the effect of bromide ion on the formation and speciation of DBPs was investigated. In fractionated Alibeyk&ouml / y source water, increasing bromide concentrations in NOM fractions increased concentrations of trihalomethanes (THMs), haloacetic acids (HAAs) and adsorbable organic halides (AOX) and resulted in a shift toward the formation of brominated species. Secondly, the impacts of SUVA and differential UV spectroscopy (&amp / #916 / UV), which has been shown to correlate well with DBP formation has been elucidated in terms of DBP formation and speciation. Alibeyk&ouml / y and Karaca&ouml / ren waters were fractionated employing various separation methods and it has been shown that SUVA did not correlate well with the formation and speciation of THMs and HAAs in tested low-SUVA waters. Similarly, no correlations were found among THMs/HAAs formations and &amp / #916 / UV. Finally, the NOM rejection performances of NF and UF membranes were investigated. NF and UF membranes (&lt / 2000 dalton) was found to be suitable for the removal NOM from surface waters having low SUVA and low bromide contents. While higher molecular weight (HMW) fraction was successfully rejected (&gt / 90%) by all membrane types, lower molecular weight (LMW) fraction could be removed with ranging efficiencies from 1.5 to 30%. NF membranes provided DOC, UV254 absorbance, THM, and HAA reductions up to 90%.

The quality of drinking water effects not only human health, but also plays a decisive role in daily life. Although the Taiwan water corporation has improved water quality of Kaohsiung in recent years and most of the random testing results of the drinking water done by the EPB could meet the drinking water standards, many people still lack confidence in the tap water. This study (1) select 500 multi-unit residences from 11 districts in Kaohsiung and survey the water quality of the indirect water supply storage devices to understand the tap water quality of indirect water distribution network in Kaohsiung. (2) Aiming at the inhabitants living in multi-unit residences, a questionnaire about the satisfaction with the tap water in Kaohsiung is undergone by random sampling in order to understand the satisfaction with the tap water of the public. (3) The monitoring values of total trihalomethanes (TTHMs) in tap water distributional network in four seasons from December 2006 to September 2007 are used to analysis the seasonal changes, the equal concentration distribution figure, and the ration of all kinds of compounds of the THMs to the total amounts. The results of above analyses can be offered to Taiwan Water Corporation to make improvement and as the references of following studies. The result of the survey of satisfaction shows that 47% people incline to use tap water as drinking water¡F53% people don¡¦t have confidence in tap water and choose to the bottled water from water stations as drinking water source. 49.1% people living in cluster housing in Kaohsiung consider the quality of tap water common¡F15.4% people are satisfied with the tap water quality and 35.7% people are not satisfied with it. The main reason is the old pipelines, and the secondary reason is about the distasteful water. Most people wish to renew old pipelines as soon as possible, and give priority to strictly control the tap water quality. The analysis result of THMs concentrations shows that the average value of THMs in each district is highest in spring and lowest in autumn, especially in Cianjhen, Siaogang, and Cijin districts. The THMs concentration distribution of Cianjhen district is higher in the spring and winter. The proportion of CHCl3 (chloroform) to total amount of THMs is the highest in the water supply network, and it is also the major source of THMs.

published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

Marginal soils, including loose sands, soft clays, and organics are not adequate materials for construction projects. These marginal soils do not possess valuable physical properties for construction applications. The current methods for remediation of these weak soils such as stone columns, vibro-compaction, etc. are typically expensive. Waste materials such as scrap tires, ash, and wastewater sludge, offer a cheaper method for stabilizing marginal soils. As an added benefit, utilizing waste materials in soil stabilization applications keeps these materials from being dumped into landfills, thereby saving already depleting landfill space. Included in this report is an extensive investigation into the current state of research on waste and recycled materials in construction applications. Also included is an investigation on actual implementation of this research in construction projects. Upon completion of this investigation, an effort was made to determine waste materials specific to the state of Florida (waste roofing shingles, municipal solid waste ash, waste tires, and paper mill sludge) that could be used in stabilizing marginal soils through soil mixing techniques. Changes in the engineering properties of soils as a result of adding these waste materials were studied and recommendations on implementing these effects into construction applications are offered.

Limited studies focused on reactions occurring during disinfection and oxidation processes of seawater. The aim of this work was to investigate disinfection by-products (DBPs) formation from the chlorination and chloramination of seawater algal organic matter and related model compounds. Simulated algal blooms directly growing in Red Sea, red tide samples collected during an algal bloom event and Hymenomonas sp. monoculture were studied as algal organic matter sources. Experiments were conducted in synthetic seawater containing bromide ion. A variety of DBPs was formed from the chlorination and chloramination of algal organic matter. Brominated DBPs (bromoform, DBAA, DBAN and DBAcAm) were the dominant species. Iodinated DBPs (CIAcAm and iodinated THMs) were detected, which are known to be highly toxic compared to their chlorinated or brominated analogues. Algal organic matter was found to incorporate important precursors of nitrogenous DBPs (N-DBPs), which have been reported to be more toxic than regulated THMs and HAAs. Isotopically-labeled monochloramine (15N- NH2Cl) was used in order to investigate the nitrogen source in N-DBPs. High formation of N-DBPs was found from Hymenomonas sp. sample in exponential growth phase, which was enriched in nitrogen-containing organic compounds. High inorganic nitrogen incorporation was found from the algal samples enriched in humic-like compounds. HAcAms formation was studied from chlorination and chloramination of amino acids. Asparagine, aspartic acid and other amino acids with an aromatic structure were found to be important precursors of HAcAms and DCAN. Factors affecting HAcAms formation (Cl2/ amino acid molar ratio and pH) were evaluated. Studies on the formation kinetics of DCAcAm and DCAN from asparagine suggested a rapid formation of DCAcAm from organic nitrogen (amide group) and a slower incorporation of inorganic nitrogen coming from monochloramine to form DCAN. High amounts of DCAN and DCAcAm were detected from the chloramination of aromatic compounds (i.e., phenol and resorcinol) indicating that N-DBPs can also be formed from organic compounds without any organic nitrogen through the incorporation of inorganic nitrogen from monochloramine. Moreover, results from Hymenomonas sp., aromatic amino acids, and phenolic compounds suggested that aromatic compounds are highly reactive with monochloramine and a major fraction of DBP precursors.

No description available.