Car exhaust catalysts were introduced in the early 1980’s, to limit the release of pollutants such as hydrocarbons, carbon monoxide and nitrogen oxides. These catalysts contain noble metals such as palladium (Pd), platinum (Pt) and rhodium (Rh) and are able to simultaneously abate all three of the above-mentioned pollutants, hence the name three-way catalyst (TWC). The exposure to high temperatures (800-1000 °C) during operation and the presence of additives in gasoline and lubricants will, after a certain time, lower the activity of the TWC. High temperatures reduce the active area by causing the noble metals to agglomerate and sinter, whereas the additives alter the activity either by fouling the pores of the support material or by interacting with the metals. The main objective of this work was to develop a method which allows for the removal of contaminants (additives) from the washcoat and enables the redispersion of the active sites (noble metals), in an effort to recover lost catalyst activity. For this purpose, regeneration experiments were carried out on a wide spectrum of different commercial car exhaust catalysts. The influence of a thermal treatment in a controlled gas atmosphere, such as oxygen or hydrogen, and a redispersing agent, e.g. chlorine, on the activity of TWC was investigated by means of laboratory-scale activity measurements. Several complementary characterization methods such as SEM/TEM, XRD, BET, LA, XPS and TPR were employed to verify the effects of the regeneration treatments on the catalyst morphology (Papers I, II). The results show that partial regeneration of catalyst activity and noble metal dispersion was achieved after thermal treatment in an oxygen-chlorine rich atmosphere at temperatures below 500 °C. A wet-chemical regeneration treatment with dilute oxalic and citric acid solutions is evaluated in Paper III. These acidic solutions are able to dissolve and remove contaminants from the washcoat, thus partly restoring the catalyst activity. An investigation of the effects of an oxy-chlorine thermal treatment for regeneration of a ‘full-scale’ commercial automotive three-way catalyst was carried out (Paper IV). Improved catalyst activity for a high mileage catalyst could be observed, with emissions lowered by approximately 30 to 40 vol.% over the EC2000 driving cycle. The properties of fresh, aged and regenerated catalysts were then studied by means of labscale experiments, on a local as well as a global level using a mathematical model (Paper V). The model allows for comparison of the intrinsic properties of the active surface by deriving and tuning parameters of a fresh catalyst and verifying the activity of a regenerated or aged catalyst. / QC 20100812

The removal of microbial populations from potable water has been a practice with great importance towards public health, as it has resulted in the reduction of literally millions of cases of infectious disease. In the United States, pathogenic organisms are most commonly removed from drinking water through the application of chlorine. Ninety-nine per cent of all U.S. potable water treatment facilities that disinfect, rely on chlorine as their sole or primary disinfectant, and over 175,000,000 Americans regularly consume chlorinated water. In 1974, Rook and Bellar et al. published studies which indicated that chlorine reacted with organic matter in water during treatment to produce a wide-range of halogenated by-products. Since that time, numerous analyses have been performed to isolate and identify the by-products of chlorination. Toxicologic and epidemiologic studies have been performed, some of which suggest that the use of chlorine as a disinfectant may be contributing to the incidence of chronic disease in the United States. Because of the concern that the use of chlorine for potable water disinfection may be contributing to chronic disease, Amendments to the Safe Drinking Water Act (SDWA) have been promulgated which strictly regulate disinfectants and disinfection by-products. Future disinfectant and disinfectant by-product regulations (1992) will have a major impact on the purveyors of potable water in the U.S.. Probably the largest challenge U.S. water treatment utilities now face is in the attempt to control for disinfectants and disinfectant by-products while maintaining the microbiological integrity of the water supply. The SDWA Amendments and their supporting regulations will result in major changes in the way water quality parameters are measured, and the way disinfection and treatment strategies are practiced. This thesis looks closely at the role of chlorine as a disinfectant, the by-products arising from chlorine reacting with organic matter, as well as the rationale behind the disinfectant and disinfectant by-product regulations. After examining the chemical, toxicologic and epidemiologic evidence which fueled the new SDWA regulations, available treatment strategies for meeting the new regulations will be detailed and examined. A water treatment strategy which best appears to maximize the reduction of waterborne disease and minimize the risk of chronic disease will then be offered. / Graduation date: 1992

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.

Aluminium smelting is a high temperature electrometallurgical process, which suffers considerable inefficiencies in power utilization and equipment maintenance. Aluminium smelting cell works in the extreme environments that contain extraordinarily aggressive gases, such as HF, CO and SO2. Mild steel used as a structural material in the aluminium industry, can be catastrophically corroded or oxidized in these conditions. This project was mainly concerned with extending the lifetime of metal structures installed immediately above the aluminium smelting cells. An aluminium-rich coating was developed on low carbon steel A06 using pack cementation technique. Yttria (Y2O3) was also used to improve the corrosion resistance of coating. Kinetics of the coating formation were studied. XRD, FESEM and FIB were employed to investigate the phase constitution and the surface morphology. Together with other potentially competitive materials, aluminium-rich coating was evaluated in simulated plant environments. Results from the long time (up to 2500h) isothermal oxidation of materials at high temperature (800??C) in air showed that the oxidation resistance of coated A06 is close to that of stainless steel 304 and even better than SS304 in cyclic oxidation tests. Coated A06 was also found to have the best sulfidation resistance among the materials tested in the gas mixture contains SO2 at 800??C. Related kinetics and mechanisms were also studied. The superior corrosion resistance of the coated A06 is attributed to the slow growing alpha-Al2O3 formed. Low temperature corrosion tests were undertaken in the gas mixtures containing air, H2O, HCl and SO2 at 400??C. Together with SS304 and 253MA, coated A06 showed excellent corrosion resistance in all the conditions. The ranking of the top three materials for corrosion resistance is: 253MA, coated A06 and SS304. It is believed that aluminised A06 is an ideal and economical replacement material in the severe corrosive aluminium smelting cell environment.

The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.

The project undertook a systematic study of chlorination of titanium oxycarbide and oxycarbonitride with the aim to develop further understanding of kinetics and mechanisms of the chlorination reactions. The project studied titania, ilmenite ores, and synthetic rutile reduced by carbon in argon and nitrogen and chlorinated at different temperatures, gas flow rates and compositions. Chlorination of titanium suboxides, iron and impurities in ilmenite was also examined. Chlorination of titanium oxycarbide Ti(O,C) or oxycarbonitride Ti(O,C,N) can be implemented at 200 to 400 deg.C, while the commercial chlorination process in the production of titanium metal or titania pigment requires 800 to 1100 deg.C. This makes chlorination of Ti(O,C) or Ti(O,C,N) an attractive technology in processing of titanium minerals. Chlorination reaction is strongly exothermal, which increased the sample temperature up to 200 deg.C above the furnace temperature. The chlorination of Ti(O,C) or Ti(O,C,N) was ignited at 150 deg.C to 200 deg.C depending on the sample composition. Their chlorination at 235 deg.C to 400 deg.C was close to completion in less than 30 min. The chlorination rate of titanium oxycarbide or oxycarbonitride increased with increasing gas flow rate. Sample composition had a significant effect on the extent of chlorination. The optimum results were obtained for titanium oxycarbide or oxycarbonitride produced with carbon to titania molar ratio of 2.5; these samples contained no detectable excess of carbon or unreduced titanium suboxides. In chlorination of reduced ilmenite ores and synthetic rutile, Ti(O,C) or Ti(O,C,N), metallic iron and Ti2O3 were chlorinated. The rate and extent of chlorination of titanium increased with increasing carbon to TiO2 ratio. Chlorination of Ti2O3 was slow relative to Ti(O,C) or Ti(O,C,N) and iron; chlorination of impurity oxides such as MgO, SiO2 and Al2O3 was not observed. The project also examined chlorination of Ti(O,C) or Ti(O,C,N) in ilmenite ore and synthetic rutile after removal of iron, which was achieved by aerated leaching of reduced samples in heated flask containing 0.37 M of ammonium chloride solution. Iron removal from the ilmenite ore or synthetic rutile resulted in higher rate and extent of chlorination of titanium oxycarbide or oxycarbonitride.

Les zéolithes représentent une importante classe de catalyseurs hétérogènes largement utilisées dans l’industrie. En effet, ce sont des catalyseurs de choix pour de multiples réactions grâce à leurs propriétés uniques largement modulables, à savoir leur forte acidité de Brønsted, leur grande surface spécifique, leur stabilité hydrothermique et leur sélectivité de forme. Cependant, la taille de leur micropores engendre des difficultés en terme de diffusion, réduisant ainsi leur potentiel catalytique. Ainsi, la conception sur mesure, en fonction de l’application finale, semble être une méthode très intéressante pour le développement de nouveaux catalyseurs zéolithiques.Les travaux réalisés au cours de cette Thèse ont pour objectif la conception de zéolithes à trois échelles : (i) au niveau du site actif en jouant sur la force acide et sur leur accessibilité, (ii) au niveau macroscopique par la taille des cristaux et (iii) au niveau du réacteur en les déposant sur divers supports. Ces différentes zéolithes ont été évaluées dans deux réactions acides : la chloration d’aromatiques et la conversion du méthanol en oléfines légères (MTO).Des zéolithes hiérarchisées ont été synthétisées selon diverses méthodes pré- ou post-Synthétiques et testées dans la chloration du nitrobenzène et du chlorobenzène. De plus, des cristaux « géant » de ZSM-5, préparés par voie fluorure, ont été évalués dans le MTO.La corrélation directe entre l’activité catalytique et les propriétés intrinsèques des zéolithes a permis de souligner les propriétés indispensables à chaque réactions. / Zeolites are aluminosilicate catalysts of great importance for the chemical industries. Their unique properties, i.e., strong Brønsted acidity, high surface area, high hydrothermal stability, and shape selectivity, combined with an extensive tunability, render them the candidate of choice in various reactions. Nevertheless, often only a fraction of their potential is exploited, due to access and diffusion limitation to/in their micropores. In this field, the rational design appears as a valuable method to design new zeolite catalysts, according to their targeted application.The work described in this Thesis aims in the design of zeolites at three levels: (i) acid site by playing on the acid strength and on the accessibility, (ii) microscopic scale by adapting the crystal size and (iii) reactor level by coating zeolite crystals on different supports. These as-Prepared zeolites were evaluated in two acid-Catalyzed reactions: the aromatics chlorination and the conversion of methanol in light olefins (MTO).Hierarchical zeolites were synthesized according to several pre- or post-Synthetic modifications and evaluated in nitro- and chlorobenzene chlorinations. Besides, “giant” ZSM-5 zeolites, prepared according to fluoride-Mediated route, as well as zeolite coatings on β-SiC, were tested in the MTO reaction.Thanks to a direct correlation between catalytic activities and intrinsic properties, optimal catalyst properties were highlighted in both reactions.

Two experiments were conducted to determine the optimal brining levels and effective chlorinated antimicrobials in three selected commercial poultry abattoirs of south Africa.The objective of the study was two fold: Firstly, the primary objective of the study was to determine the optimal inclusion level of brine for application in chicken processing to elongate the shelf life by reducing spoilage bacteria under refrigeration stage while the secondary objective of the study was to determine the most effective chlorinated antimicrobial to be applied in poultry processing plants to reduce spoilage bacteria. For each experiment, a complete randomized design was used. The general linear model procedure was used to determine the effects of brining and chlorine antimicrobials on the Psychrotrophic bacterial load of individually quick frozen (IQF) chicken portions. Simultaneously, a quadratic type equation was used to determine the optimal inclusion level of brine in relation to the responses of Psychrotrophic bacterial loads. The results indicated that control samples (0% brine) had higher (P < 0.05) bacterial load than all samples injected with various injection levels. There were significant differences (P < 0.05) between samples injected with 15% and 20% for all major abattoirs combined. However, there were no differences (P > 0.05) between samples injected with 20% and 25% brine, respectively. In addition, there was a significant difference (P < 0.05) in Psychrotrophic bacterial load between the samples treated with 25% and 30% brine inclusion level as well as those treated with 30% and 35% brining levels in all abattoirs. Futhermore, the results of the study also showed that Acidified Sodium Chloride had significantly lower bacterial load than both aqueous chlorine and chlorine dioxide. However, the effect of percentage brining on average Psychotrophic bacterial count had minimum quadratic values of 24.45 – 0.517 brining + 0.805 brining2 with r = 0.995; r2= 0.989, with optimum percentage brining dose being 43.08%. By extension, the result implies that the lowest reduction in spoilage bacteria is attained at 43.08% of brine inclusion level. These findings have implications on the most effective and convenient antimicrobial to be used in chicken abatoirs as well as reduction of psychotrophic bacterial load on individually quick frozen (IQF) chicken portions / Agriculture, Animal Health and Human Ecology / M. Sc. (Agriculture)

[pt] Este trabalho aborda um estudo alternativo voltado para o tratamento de um resíduo industrial gerado durante a fabricação de aço nos fornos elétricos, através do uso reagentes cloretantes. O resíduo analisado quantitativamente apresenta os seguintes resultados em relação aos seus principais constituintes: 29 por cento de Fe e 16 por cento Zn. Tem-se como principal objetivo uma recuperação do zinco contido e o simultâneo enriquecimento do resíduo em Fe2O3, que permitiria, então, o reaproveitamento do resíduo pela indústria e a conseqüente diminuição do impacto ambiental. Foram utilizados diversos métodos de análise de caracterização, tais como difração de raios-X, microscopia eletrônica de varredura, difração e fluorescência de raios-X e espectroscopia de massa (ICPMS). Observou-se que o zinco encontra-se presente na amostra na forma de ferrita de zinco (franklinita). As análises prévias dos clássicos diagramas energia livre de Gibbs versus T em variadas opções de tratamentos químicos indicaram que algumas ustulações, tais como aquelas com Cl2 e CaCl2, seriam capazes de viabilizar a remoção seletiva do zinco, enriquecendo assim o resíduo em ferro, a fim de que possa ser usado novamente na alimentação do forno. Os resultados experimentais da ustulação com cloreto de cálcio confirmaram tal possibilidade ao mostrar que quando a reação é conduzida a 1100 graus Celsius durante 30 minutos com um excesso de 40 por cento de reagentes, o teor de ferro no resíduo aumenta ligeiramente (com remoção de 21 por cento), enquanto o teor de zinco decresce de 16 por cento para 1 por cento (remoção de 94 por cento), sugerindo estudos complementares onde a seletividade fosse otimizada. / [en] This work is related to an alternative chemical treatment of an electric furnace dust. The residue containing 29 percent of Fe and 16 percent of Zn, most of it in a zinc ferrite (ZnFeO4) structure, was submitted to chlorine containing reagents. The main idea was to separate the zinc from the iron through a selective chloride formation of the former followed by its volatilization. In this case, the residue, without the zinc presence, could be reused in the industrial plant, minimizing the environmental impact. Some characterization analyze methods was used as Xray diffraction, scanning electronic microscopy, diffraction and X-ray fluorescence and mass spectroscopy (ICP-MS). The zinc observed in the sample was present as zinc ferrite (franklinite). Preliminary thermodynamics studies have shown that chlorine and calcium chloride roasting could act selectively on the residue, then producing the volatile zinc chloride and leaving behind the iron oxide. Experimental work has proved that possibility showing that when the reaction happened at 1100 degrees Celsius, with 40 percent the reagents excess, for 30 minutes, the iron content increase slowly (with 21 percent removed) while that the zinc conten decrease the 16 to 1 percent (94 percent removed), proposing complementaries studies to optimize the selectivity.

Die 17 Elemente der Seltenen Erden sind Bestandteil vieler Hochtechnologieprodukte, wie Elektromotoren, Spezialgläsern oder Katalysatoren, dennoch liegt die Recyclingrate aus End-of-Life-Produkten derzeit unter 1 %. Mit der Feststoffchlorierung wurde im Rahmen dieser Arbeit eine chemikalien- und kostensparende Methode für den Aufschluss Seltener Erden aus Leuchtstoff- und Magnetabfällen untersucht. Dabei wurden die gemahlenen Edukte mit NH4Cl vermischt und anschließend im Drehrohrofen erhitzt. Durch thermische Zersetzung des NH4Cl wird HCl- und NH3-Gas freigesetzt. Ersteres überführt die Seltenen Erden in die wasserlöslichen Metallchloride, während der NH3 im Prozess als Lösung in 5N-Reinheit anfiel. Die Seltenerdausbeuten lagen je nach Ausgangsstoff zwischen 83,9 und 99,9 %. Die Optimierung der Feststoffchlorierung erfolgte anhand statistischer Versuchspläne, wodurch neue, überraschende Erkenntnisse im Hinblick auf Reaktionsverläufe, Selektivitäten und Prozessführung gewonnen werden konnten.