<p>There is an increased discharge of produced water in the USA, which is causing decrease in the amount of usable water and is being rendered useless by refinery and extraction operations. Produced water that is obtained from these activities is usually not feasible to be used in any form. So, it becomes necessary to get the water to a quality standard, as per the US EPA, which will make this water suitable for both commercial as well as household purposes.</p><p> </p><p>There have been a number of studies on Au, Ag and Carbon Nanotubes solar enabled steam generation with potential applications in water purification, distillation and sterilization of medical equipment. The key challenge with these nanoparticles is cost of production, hence limiting its wide application for clean water production. This work, for the first time, reports on activated carbon enabled steam generation hence addressing the cost limitations of metallic nanoparticles. Activated carbon has high solar absorptivity at various wavelengths of visible light.</p><p> </p>This work uses Activated Carbon coated Polyurethane foam to simultaneously adsorb oil from the produced water and also yield surface vapors under application of solar light to get a clean distillate which can be used in various ways be it commercial or household. The given fabricated system will be an inexpensive and simple method to get clean water. The temporal evolution of the distillate has been measured as well as the temperature characteristics. Experiments were carried out using activated carbon and CNT nanofluids and polyurethane membrane with immobilized activated carbon and CNT. A simulated solar light of 1 KW ~1 Sun was used. The rate of evaporation, temporal and spatial evolution of bulk temperature in the water were monitored automatically and recorded for further data reductions. Parametric studies of the effect of nanoparticle concentration, water quality and salinity were performed. Experimental evidence showed that activated carbon has potential. Previous work reported for the first time that optimal activated carbon concentration for maximum steam generation is 60 % vol. There was a 160 % increase in steam production rate at 60 % concentration of activated carbon when compared with D.I. water.Different atmospheric conditions were varied and the concentration of the sun to see the effects on the production of water. The recovery capacity of the foam was also tested so as to determine the waste oil that can be obtained from the foam and if the foam can be reused without being disposed of. More than 95% oil can be recovered The quality analysis has been performed and is an integral focus of the work as the comparison with the USA EPA (Environmental Protection Agency) will make it more robust and real world ready. The inclusion of Polyurethane foam, which is a major accumulating waste in the environment because of its use in packaging industry, and solar light as the energy source, to drive the distillation process, makes this a very clean and green process to treat produced water.

Le biométhane est une source d'énergie verte qui, de part son coût et son faible impact environnemental, peut être considéré comme une alternative au gaz naturel et au diesel. La production d'énergie primaire par l'Union Européenne, à partir du biométhane, a été multipliée par 23 en cinq ans (2011-2016), ce qui rend nécessaire et urgent la recherche de nouvelles solutions performantes pour l’épuration du biogaz, notamment la séparation du dioxyde de carbone (CO2) du méthane (CH4).Dans ce contexte, l’objectif de ce travail doctoral porte sur la détermination des indicateurs de performances (capacité d’adsoprtion, sélectivité) de charbons actifs (CAs) dans le contexte de la séparation méthane/dioxyde de carbone pour la production de biométhane. A cette fin, les isothermes d'adsorption de CH4 et CO2 ont été déterminées à partir d’un dispositif manométrique d’adsorption. Les mesures ont été effectuées à des températures de 303 et 323 K pour des pressions variant de 0.1 à 3 MPa. Dans un premier temps, l’étude a porté sur 5 échantillons commerciaux de CA différents. Les résultats montrent une corrélation entre la surface spécifique et la quantité de dioxyde de carbone adsorbée. En outre, le volume microporeux a un impact significatif lors des processus d'adsorption du CO2 tandis que le volume des mésopores n'a pas d’effet direct.Par ailleurs, l'étude complémentaire d'isothermes d'adsorption du CH4 et du CO2 purs à l’aide de trois charbons actifs, issus de noyaux d’olive, activés par différentes méthodes de synthèse, révèle que la méthode d'activation est déterminante pour modifier les propriétés chimiques et structurales des charbons actifs et donc accroitre leurs propriétés d'adsorption.En outre, la sélectivité des CAs commerciaux pour la séparation CH4/ CO2 a été calculée à partir des isothermes d'adsorption du mélange équimolaire CH4/ CO2 à une température de 303 K et pour des pressions jusqu'à une pression de 3 MPa. Les résultats obtenus montrent qu’une surface spécifique élevée (< 1500 m2 g-1) facilite l'adsorption du CO2 mais réduit le facteur de sélectivité. En parallèle, une forte porosité conduit à une séparation moins efficace des deux gaz alors que la présence de groupes basiques en surface favorise les phénomènes d’adsorption du CO2.L'ensemble des résultats montre que les charbons actifs, étudiés dans ce travail de recherche, possèdent des propriétés d'adsorption comparables à celles des charbons actifs commerciaux et sont des matériaux compétitifs pour l'épuration du biogaz. / Biomethane is a proven source of clean energy, it is one of the most cost-effective and environment-friendly substitute for natural gas and diesel. The European Union primary energy production from biomethane has folded by ~23 times in a 5 years time period (2011-2016) making necessary to find new and improved solutions for the separation of methane (CH4) and carbon dioxide (CO2), main components of biogas. In this context, the objective of this doctoral thesis is the determination of performance indicators such as the adsorption capacity and selectivity of activated carbons (ACs) for the CH4/ CO2 separation. This work focuses on the adsorption properties of activated carbons for the methane/carbon dioxide separation. To this end, CH4 and CO2 pure gas experimental adsorption isotherms of activated carbons were obtained on a pressure range of 0.1 to 3 MPa) and temperatures ranging from 303 to 323 K. The first part of this thesis project consisted in the analysis of the CH4 and CO2 pure gas adsorption properties of 5 commercial activated carbons Using a set of five commercial activated carbons a linear relationship between the adsorbent surface area and the CO2 adsorption capacity was determined. The micropore volume also showed a direct influence on the adsorption capacity. The second part of this work consisted in the study of the carbon dioxide and methane adsorption behavior of biomass-based activated carbons. Using a series of 3 ACs that had been obtained from olive stones by different activation methods, the activation technique proved to be of mayor importance as it determines the textural and chemical properties of the adsorbent and thus its gas adsorption capacity.Lastly, the CH4/CO2 adsorption selectivity of the 5 commercial activated carbons was calculated from the equimolar mixture adsorption isotherms. The selectivity factor was proven to be dependent on the sum of textural and chemical properties of the samples. Although, activated carbons with high average pore sizes and surface areas depicted higher adsorbed quantities it was on detriment of their selectivity. The selectivity was found to be better for the activated carbon showing an intermediate surface area and a narrow pore size distribution. In addition, the presence of sulfur functionalities was also found to improve the adsorption selectivity. Overall, this work shows that activated carbons are competitive materials for the upgrading of biogas, displaying adsorption properties comparable to those of other commercially available materials.

This thesis deals with diffusion and flow of sub-critical hydrocarbons in activated carbon by using a differential permeation method. The hydrocarbons are selected according to the effect on environmental concerns and their unique characteristics such as polarity and affinity towards activated carbon. Although it has been known that transport processes in activated carbon consist of Knudsen diffusion, gaseous viscous flow, adsorbed phase diffusion (so called, surface diffusion) and condensate flow, there have been no rigorous models to describe the transport processes in activated carbon with a full range of pressures. In particular among the four processes, the mechanism of adsorbed phase diffusion in activated carbon is still far from complete understanding. Also due to the dispersion interactions between adsorbing molecules and the solid surface, one would expect that Knudsen diffusion is influenced by the dispersive forces. From intensive experimental observations with a great care over a full range of pressures, conventional methods (for example, direct estimation from inert gas experiments) to determine adsorbed phase diffusion are found to be inadequate for strongly adsorbing vapors in activated carbon. By incorporating the effect of adsorbate-adsorbent interactions into Knudsen diffusivity, the general behavior of adsorbed phase diffusion in terms of pressure (or surface loading) can be obtained, showing a significant role in transport at low pressures. For non-polar hydrocarbons such as benzene, carbon tetrachloride and n-hexane, a mathematical model, which accounts for the effects of adsorbate-adsorbent interactions and pore size distribution, is formulated and validated, resulting in a good agreement with experimental data. Moreover, the adsorption and dynamic behaviors of alcohol molecules (which are polar compounds) are investigated with an aim to compare their behaviors against those of non-polar compounds.

A vast number of sites that have been contaminated by industrial activities have been identified worldwide. Many such sites now pose serious risks to humans and the environment. Given the large number of contaminated sites there is a great need for efficient, cost-effective  remediation methods. Extensive research has therefore been focused on the development of such methods. However, the remediation of old industrial sites is challenging, for several reasons. One major  problem is that organic contaminants become increasingly strongly sequestered as they persist in the soil matrix for a long period of time. This process is often referred to as ‘aging’, and leads to decreasing availability of the contaminants, which also affects the remediation efficiency. In the work underlying this thesis, the influence of soil and contaminant properties on the efficiency of various physical and chemical soil remediation methods was investigated. The investigated contaminants were polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Briefly, the results show that as the size of soil particles decreases the contaminants become more strongly sorbed to the soil’s matrix, probably due to the accompanying increases in specific surface area. This affected the efficiency of the removal of organic pollutants by both a process based on solvent washing and processes based on chemical oxidation. The sorption strength is also affected by the hydrophobicity of the contaminants. However, for a number of the investigated PAHs their chemical reactivity was found to be of greater importance for the degradation efficiency. Further, the organic content of a soil is often regarded as the most important soil parameter for adsorption of hydrophobic compounds. In these studies the effect of this parameter was found to be particularly pronounced for the oxidation of low molecular weight PAHs, but larger PAHs were strongly adsorbed even at low levels of organic matter. However, for these PAHs the degradation efficiency was positively correlated to the amount of degraded organic matter, probably due to the organic matter being oxidized to smaller and less hydrophobic forms. The amount of organic matter in the soil had little effect on the removal efficiency obtained by the solvent-washing process. However, it had strong influence on the performance of a subsequent, granular activated carbon-based post-treatment of the washing liquid. In conclusion, the results in this thesis show that remediation of contaminated soils is a complex process, the efficiency of which will be affected by the soil matrix as well as the properties of the contaminants present at the site. However, by acquiring thorough knowledge of the parameters affecting the treatability of a soil it is possible to select appropriate remediation methods, and optimize them in terms of both remediation efficiency and costs for site- and contaminant-specific applications.

The presence of micropollutants, particularly pesticides, in surface waters across Canada has been of concern not only for their environmental impact, but also for their potential effects on human health and recalcitrant nature to conventional water treatment methods. Although ozone has been mainly applied for disinfection of drinking water, oxidation of trace organics by ozonation has been considered potentially effective. In an effort to meet increasingly stringent drinking water regulations, different solid catalysts have been used to enhance the removal of water contaminants by ozonation. In spite of the increasing number of data demonstrating the effectiveness of heterogeneous catalytic ozonation, the influence of different factors on the efficiency of micropollutants oxidation is still unclear.<p> In the present work, application of three solid catalysts in ozonation of two model micropollutants in pure water was examined using a laboratory-scale reaction system over a range of operating conditions. The three catalysts investigated were activated carbon, alumina, and perfluorooctyl alumina, and the two model micropollutants were the pesticides atrazine and 2,4-dichlorophenoxyactic acid. The effects of solution pH, presence of a radical scavenger, pesticide adsorption on catalyst, and catalyst dose on micropollutant removal were investigated. Solution pH was found to significantly influence the catalyst ability to decompose ozone into free hydroxyl radicals. The effect of these free radicals was markedly inhibited by the radical scavenger resulting in a negative impact on pesticides degradation. In general, the removal rate of pesticides was found to increase with increasing doses of catalyst.<p> In the ozonation process in the presence of activated carbon, atrazine removal rates increased four and two times when using a catalyst dose of 0.5 g L-1 at pH 3 and 7, respectively, whereas observed reaction rates for 2,4-D increased over 5 times in the presence of 1 × 10-4 M tert-butyl alcohol at pH 3. In the ozonation system catalyzed by 8 g L-1 alumina, the observed reaction rate constant of atrazine removal notably improved at neutral pH by doubling the micropollutant removal rate. For the pesticide 2,4-D in the presence of 1 × 10-4 M tert-butyl alcohol at pH 5, the observed removal rate was over ten times higher than that for the non-catalytic ozonation process using also using a catalyst dose of 8 g L-1. Modification of alumina to produce perfluorooctyl alumina resulted in a material able to significantly adsorb atrazine, while not exhibiting affinity for adsorption of 2,4-D. In spite of its adsorptive properties, perfluorooctyl alumina was found to enhance neither molecular ozone reactions nor ozone decomposition into hydroxyl radicals. Thus, the observed removal rates for atrazine and 2,4-D by ozonation in the presence of perfluorooctyl alumina did not increase significantly.

An electrochemical double-layer capacitor (EDLC) is a potential buffer for current power and energy supply. In this work, activated carbon derived from fluid coke as a brand new electrode material was studied due to its high specific surface area (SSA) and large portion of mesopores. A suitable electrode material formula, current collector, and cell configuration were investigated to fabricate a testable system and ensure the reproducibility of measurements. Cyclic voltammetry (CV) and constant current charge/discharge (CD) techniques were used to characterize the performance of the electrode material, as well as to study its fundamental behaviour. A new procedure was established for quantifying the capacitance (Cc) of EDLC from CV which isolates the effect of internal resistance on the measured capacitance (CM). The specific capacitance of single electrode made of activated carbon (~1900 m2/g) with approximately 80% mesopores and macropores was able to reach 180 F/g at scan rate of 0.5mV/s.

Due to the water pollution problems created by MTBE, significant research was focused on the production of alternative oxygenates, such as ethyl tert-butyl ether (ETBE), tert-amyl-methyl-ether (TAME) and tert-amyl-ethyl-ether (TAEE) as octane enhancing gasoline blending components. These oxygenates are expected to improve the burning characteristics of gasoline and reduce exhaust emissions of CO and hydrocarbons. Generally, macroreticular acidic resin catalysts (Amberlyst-15) are used for the etherification reactions between C5 iso-olefins (2M1B/2M2B) and alcohols (ethanol/methanol). But in recent years, heteropoly acid compounds are being used in the production of tert-ethers to replace those macroreticular acidic resin catalysts. HPAs are known to be active catalysts for many of homogeneous and heterogeneous acid catalyzed reactions.These compounds have high acidity, high catalytic activity but they are highly soluble in polar solvents such as water,alcohol when they are used in bulk form. In this research, applicability of bulk heteropoly acid (HPA) and its supported form, to the gas-phase etherification reaction of iso-olefin (2-methyl- 2-butene) with ethyl alcohol in a continuous differential reactor was investigated. The heteropoly acid (H3PW12O40.xH2O) was supported on activated carbon, at two different loading levels, by aqueous impregnation technique. After catalyst characterization, kinetic experiments were done in a temperature range between 80&deg / C-97&deg / C with a feed concentration of 30 vol.%2M2B+70 vol.% ethanol. Supported HPA catalysts yielded lower conversion and rate of reaction than the bulk HPA. After that, to make a comparison, same experiments have been carried out with Amberlyst-15 and a different HPA (H3PMo12O40.xH2O) at 90oC. The results showed that, at this temperature, bulk tungstophosphoric acid (H3PW12O40.xH2O) was highly active among the other catalysts. Moreover, the deactivation of bulk and supported HPA were investigated and found that partial deactivation occurred when they were reused, without any treatment. In the final part of the study, the activity of alcohol-treated supported HPA catalyst and formation of side products, dimethyl or diethyl ether, at 90&deg / C were investigated. When the supported catalyst was treated with alcohol, before utilizing in the experiments, lower conversion was obtained with respect to the conversion value obtained in the presence of fresh catalyst. The studies done on the formation of side product showed that, no side product was formed at this working temperature.

An electrochemical double-layer capacitor (EDLC) is a potential buffer for current power and energy supply. In this work, activated carbon derived from fluid coke as a brand new electrode material was studied due to its high specific surface area (SSA) and large portion of mesopores. A suitable electrode material formula, current collector, and cell configuration were investigated to fabricate a testable system and ensure the reproducibility of measurements. Cyclic voltammetry (CV) and constant current charge/discharge (CD) techniques were used to characterize the performance of the electrode material, as well as to study its fundamental behaviour. A new procedure was established for quantifying the capacitance (Cc) of EDLC from CV which isolates the effect of internal resistance on the measured capacitance (CM). The specific capacitance of single electrode made of activated carbon (~1900 m2/g) with approximately 80% mesopores and macropores was able to reach 180 F/g at scan rate of 0.5mV/s.

The presence of micropollutants, particularly pesticides, in surface waters across Canada has been of concern not only for their environmental impact, but also for their potential effects on human health and recalcitrant nature to conventional water treatment methods. Although ozone has been mainly applied for disinfection of drinking water, oxidation of trace organics by ozonation has been considered potentially effective. In an effort to meet increasingly stringent drinking water regulations, different solid catalysts have been used to enhance the removal of water contaminants by ozonation. In spite of the increasing number of data demonstrating the effectiveness of heterogeneous catalytic ozonation, the influence of different factors on the efficiency of micropollutants oxidation is still unclear.<p> In the present work, application of three solid catalysts in ozonation of two model micropollutants in pure water was examined using a laboratory-scale reaction system over a range of operating conditions. The three catalysts investigated were activated carbon, alumina, and perfluorooctyl alumina, and the two model micropollutants were the pesticides atrazine and 2,4-dichlorophenoxyactic acid. The effects of solution pH, presence of a radical scavenger, pesticide adsorption on catalyst, and catalyst dose on micropollutant removal were investigated. Solution pH was found to significantly influence the catalyst ability to decompose ozone into free hydroxyl radicals. The effect of these free radicals was markedly inhibited by the radical scavenger resulting in a negative impact on pesticides degradation. In general, the removal rate of pesticides was found to increase with increasing doses of catalyst.<p> In the ozonation process in the presence of activated carbon, atrazine removal rates increased four and two times when using a catalyst dose of 0.5 g L-1 at pH 3 and 7, respectively, whereas observed reaction rates for 2,4-D increased over 5 times in the presence of 1 × 10-4 M tert-butyl alcohol at pH 3. In the ozonation system catalyzed by 8 g L-1 alumina, the observed reaction rate constant of atrazine removal notably improved at neutral pH by doubling the micropollutant removal rate. For the pesticide 2,4-D in the presence of 1 × 10-4 M tert-butyl alcohol at pH 5, the observed removal rate was over ten times higher than that for the non-catalytic ozonation process using also using a catalyst dose of 8 g L-1. Modification of alumina to produce perfluorooctyl alumina resulted in a material able to significantly adsorb atrazine, while not exhibiting affinity for adsorption of 2,4-D. In spite of its adsorptive properties, perfluorooctyl alumina was found to enhance neither molecular ozone reactions nor ozone decomposition into hydroxyl radicals. Thus, the observed removal rates for atrazine and 2,4-D by ozonation in the presence of perfluorooctyl alumina did not increase significantly.

In this study, we developed the manufacturing pathways of carbon nanofibers (CNF) and activated carbon nanofibers (ACNF) via the ¡§melt-spinning¡¨ method. A novel route based on the solvent-free core/sheath melt-spinning of polypropylene/ (phenol formaldehyde-polyethylene) (PP/(PF-PE)) to prepare CNF. The approach consists of three main steps: co-extrusion of PP (core) and a polymer blend of PF and PE (sheath), followed by melt-spinning, to form the core/sheath fibers; stabilization of core/sheath fibers to form the carbon fiber precursors; and carbonization of carbon fiber precursors to form the final CNF. Both scanning electron microscopy and transmission electron microscopy images reveal long and winding CNF with diameter 100 - 600 nm and length greater than 80 £gm. With a yield of ~ 45 % based on its raw material PF, the CNF exhibits regularly oriented bundles which curl up to become rolls of wavy long fibers with clean and smooth surface. Results from X-ray diffractometry, energy dispersive X-ray, Raman spectroscopy, and selected area electron diffraction patterns further reveal that the CNF exhibits a mixed phase of carbon with graphitic particles embedded homogeneously in an amorphous carbon matrix. The carbon atoms in CNF are evenly distributed in a matrix having a composition of 90 % carbon element and 10 % in oxygen element. A series of ACNF have also been prepared based on the chemical activation on the thus-prepared CNF; their morphological and microstructure characteristics were analyzed by scanning electron microscopy, atomic force microscopy (AFM), Raman spectroscopy, and X-ray diffractometry, with particular emphasis on the qualitative and quantitative AFM analysis. The effect of activating agent, potassium hydroxide and phosphorous acid, is compared; factors affecting the surface morphology and microstructure of ACNF are analyzed. The ACNF also exhibits a mixed phase of carbon with graphitic particles embedded homogeneously in an amorphous carbon matrix. The resulting ACNF consists of 73 % C element and 27 % O element. The total pore volume of the all activated ACNF is larger than that of un-activated CNF. It can be inferred that chemical activation by KOH results in increased micropore volume in carbon nanofibers; while the micropores produced by the chemical activation of H3PO4 may further be activated and then enlarged to become the mesopores at the expense of micropore volume. For the concentration effect of KOH on ACNF, it can be inferred that high concentration KOH activation results in increased SBET and micropore volume in carbon nanofibers. The average pore diameter of ACNF gradually decreases as the KOH concentration increases.