The study combined photoelectrocatalytic technology (PEC) with electrical glassfiber filter (EGF) to decompose volatile organic compounds (VOCs). External electrical voltage was applied to retard the recombination of electron-electron hole pairs and increase the surface temperature of the photocatalysts coated on the electrical glassfiber filter, which could further decompose VOCs more effectively via photoelectrocatalytic technology. Acetone was selected as the gasous pollutant for this particular study. A commercial TiO2 photocatalyst (AG-160) was coated on GFF via impregnation to decompose acetone in a batch PEC reactor. Operation parameters investigated in this study included acetone concentration (50~400 ppm), electrical voltage (0~6,500V), water content (0~20,000 ppm), reaction temperature (40¢J~80¢J).The incident UV light of 365 nm wavelength was irradiated by three 15-wat low pressure mercury lamps (£f=365 nm) placing above the batch PEC reactor. The TiO2-coated EGF was placed at the center of the batch PEC reactor. Acetone was injected into the reactor by a gasket syringe to conduct the PEC decomposition test. Acetone was analyzed quantitatively by a gas chromatography with a flame ionization detector (GC/FID). Finally, a Langmuir-Hinshelwood kinetic (L-H) model was proposed to simulate the PEC reaction rate of acetone. Experimental results showed that the size range of the self-produced nano-sized photocatalyst prepared by sol-gel was 35~50 nm. Three duplicate tests of PC and PEC degradation of acetone indicated that TiO2 was not deactivated during the PC and PCE reactions, hence TiO2 can be reused in the experiments. Results obtained from the PC and PEC degradation experiments indicated that the PEC reaction rate was higher than the PC reaction rate.The PEC reaction rate increased with applied electrical voltage, and the highest decomposition efficiency occurred at 6,500 V. Electrical field generated by the differences of electrical voltage can effectively enhance the oxidation capability of TiO2 since electron (e-) can be conducted to retard the recombination of electron and electron hole pairs. Both PC and PEC technologies could be used to decompose acetone. Among them, PEC had highter decomposition efficiency of acetone than PC up to 34%. Rsults obtained from the operation parameter tests reaveled that raising electrical voltage could enhance the decomposition efficiency of acetone only for electrical voltages above 2,000 V. However, the decomposition efficiency of acetone tended to level off as electrical voltage became higher. Zero-order reaction rate of the PEC reaction was observed for initial acetone concentration of 100~400 ppm, while the PEC reaction decreased gradually for initial acetone concentration reaction below 100 ppm. It revealed that the PEC reaction was pseudo ozero-order for initial acetone concentration of 100~400 ppm, and pseudo first-order reaction for acetone concentration below 100 ppm. Additionally, the PC reaction rate increased with temperature at 45-80¢J. However the PEC reaction rate increased with temperature at 45-60¢J, and decreased with temperature at 60-80¢J. An adsorptive competition between acetone and water molecules at the active sites over TiO2 surface caused either promotion or inhibition of TiO2 decomposition depending on moisture content . For the PC and PEC reactions, the optimum operating condition of water vapor concentration was 10,000 ppm, but inhibition occurred when the water vapor concentration increased up to 20,000 ppm. Finally, the Langmuir-Hinshelwood kinetic model was applied to investiage the influences of reaction temperature, initial concentration of acetone, and water content on the photoelectrocatalytic reaction rate of acetone. Model simulation results showed that photoelectrocatalytic reaction rate constant of acetone(kLH) and adsorptive equilibrium constant(KA) increased with electrical voltage and acetone initial concentration. This study sevealed that experimental and simulated results were in good agreement. Thus, PEC reaction rate of acetone on the surface of TiO2 can be also succesfully simulated by the L-H kinetic model.

Adsorption/desorption behaviors of three volatile organic compounds (VOCs) emitted from the optoelectronics industry by Y-type and ZSM-5 zeolites were studied in this work. Target VOCs include acetone, isopropyl alcohol (IPA), and propylene glycol monomethyl ether acetate (PGMEA). Adsorption/desorption experiments were conducted in a fixed-bed column using various operating conditions to mimic the commercial ones. Also studied include the adsorption kinetics for single-component, two-component, and three-component cases. Experimental results of the single-adsorbate case by both model zeolites have shown that the amount of VOC adsorbed follows the order of PGMEA > IPA > Acetone. This is ascribed to the greatest molecular weight of PGMEA among three VOCs tested. The adsorption capacity of each zeolite for each target VOC was found to increase with its increasing initial concentration. Freundlich isotherm and Langmuir isotherm were found to be suitable for describing the adsorption behaviors for the single-adsorbate case. Results of the desorption experiments also showed that most of the target VOCs could be desorbed at 180¢J in 100 minutes. The adsorption capacities of the regenerated model zeolites were found to be decreasing as the regeneration times increased. As compared with the fresh ones, the regenerated zeolites had reduced specific surface areas, but increased pore sizes. In addition, the Yoon and Nelson equation was employed to study the kinetic behaviors of adsorbing the target VOCs by the model zeolites. A good agreement of the experimental results and predictions by the Yoon & Nelson model was obtained for the single-adsorbate case. However, the Yoon and Nelson model was found to be incompetent to simulate and predict all the multi-adsorbate cases including two-component adsorption and three-component adsorption in this work. Again, it is speculated that the displacement of lower-molecular-weight adsorbates (i.e., acetone and IPA) by PGMEA (an adsorbate of a much greater molecular weight) would be responsible for this finding. For the two-adsorbate case, nevertheless, the Yoon and Nelson equation was found to be capable of describing the adsorption behavior under the circumstance of C/C0 < 1.

The study of catalytic oxidation on the removal of NO was investigated over the Cu-catalysts . The Cu-catalysts , including Cu/TiO2 , Cu/Al2O3 and Cu/SiO2 , were prepared by impregnation method . Alougth NO2 , the product of this reaction , has higher toxicity than NO , but it might be removed completely by absorption with H2O or alkalinal solution for its high solubility . The experiments can be divided into three parts , i.e. , the screen of test catalysts , the effect of operating factors on the conversion of NO and the kinetic model . In the first part , the activity of test catalysts , which were prepared by mixing three various sources of Cu-ions¡]i.e., Cu(NO3)2 , Cu(CH3COO)2 , and CuSO4¡^with three different types of support¡]i.e., TiO2 , Al2O3 , and SiO2¡^, and were compared in form of conversion on NO to find the best catalyst . The results show that the mixture Cu(NO3)2 / TiO2 has the good performance on the conversion of NO , and also has more wider operating in range of temperature . In order to find the optimal loading of Cu on Cu(NO3)2 / TiO2 , additional test of various dosage over the catalysts was conduct in series . It is found that 8wt.% of Cu loading on Cu(NO3)2 / TiO2 is the most economic dosage . Therefore , we select this type of Cu oxide as the best catalyst in the following work . In the second part , the effect of NO inlet concentration , space velocity and humidity on the conversion of NO were performed . The results show that the conversion of NO decreases with the increasing of [NO]in when [NO]in is larger than 1000ppm¡Fthe conversion of NO is not changed with [NO]in when [NO]in is lower than 1000ppm . The better space velocity is 15000hr-1 , i.e.,the empty bed residence time is 0.24 second . The reaction on NO conversion would be restrained by higher humidity contenting in inlet gas stream , but the effect of inhibition on NO conversion is not significant . Finally , the kinetics of the oxidation of NO over 8wt.% Cu(NO3)2 / TiO2 was obtained by integral method .It is found that the oxidations of NO can be described by first order reversible reaction and the observed activation energy are 15.8 kcal/mole¡]forward reaction¡^and 25.9 kcal/mole¡]backward reaction¡^, respectively . By comparing the conversion of predicted NO with the experimentals , we can find the suitable operation conditions in application of the kinetic model : the inlet concentration of NO in a range of 300-1000ppm , the empty-bed residence time ranging from 0.12-0.48 second , and the absolute humidity ranging from 4854 to 42475ppm .

This study investigated the photocatalytic reduction of CO2 in a self-designed closed circulated batch reactor system and a bench-scale batch photocatalytic reactor. The photocatalysts tested included titanium dioxide (TiO2, Degussa P-25) and zirconium oxide (ZrO2). The reductants investigated included hydrogen (H2), water vapor (H2O), and hydrogen plus water vapor (H2+H2O). The wavelengths of incident near ultra-violet (UV) and UV lights for the photocatalysis of TiO2 and ZrO2 were 365 nm and 254 nm, respectively. The initial concentrations of CO2 ranged from 0.2-5.0% and the reaction temperature ranged from 35-95 ¡³C. The incident near-UV (or UV) light with wavelength of 365 nm (or 254 nm) was irradiated by a 15-watt low-pressure mercury lamp. The photocatalytic reaction was conducted continuously for approximately two hours. Reactants and products were analyzed by a gas chromatography with a flame ionization detector followed by a methanizer (GC/FID-methanizer). Experimental results indicated that glass pellets coated with TiO2 had better photoreduction efficiency than ZrO2. The highest yield rates of the photoreduction of CO2 were obtained using TiO2 with H2+H2O and ZrO2 with H2. Photoreduction of CO2 over TiO2 with H2+H2O formed CH4, C2H6, and CO in the yield of 32.95~94.60, 0.80~18.55, 1.12~21.78 £gmol/g, respectively, while the photoreduction of CO2 over ZrO2 with H2 formed CO in the yield of 0.34~4.99 £gmol/g. Results obtained from the operating parameter tests showed that the photoreduction rate increased with the initial concentration of carbon dioxide and resulted in more product accumulation. The photoreduction rate of carbon dioxide increased with reaction temperature, which promoted the formation of products. Concurred with previous researches, the reaction rate of major products over TiO2 and ZrO2 were higher than previous investigations of CO2 photoreduction. Furthermore, the spectra of FTIR showed that formic acid (HCOOHads), methanol (CH3OHads), carbonate (CO32−ads), bicarbonate (HCO32−ads), formate (HCOO−ads), formic acid (HCOOH ads), formaldehyde (HCOHads) and methyl formate (HCOOCH3 ads) formed on the surface of TiO2 and ZrO2 photocatalysts. The detected reaction products supported the proposal of two reaction pathways for the photoreduction of CO2 over TiO2 and ZrO2 with H2 and H2O, respectively. A modified bimolecular Langmuir-Hinshelwood kinetic model was developed to simulate the reaction temperature, CO2 initial concentration and relative humidity promotion and inhibition of the photoreduction of CO2. Additionally, the modified L-H kinetic model was successfully applied to simulate the photoreduction rate of CO2. The result showed that CO2 could be reduced by used solar light over TiO2 and ZrO2 photocatalysts. The reaction products of CO2 photoreduction over TiO2 were CH4, C2H6, and CO in the yield of 2.16~2.995, 0.057~0.128, 0.078~0.134 £gmol/g, respectively, while the photoreduction of CO2 over ZrO2 formed only CO in the yield of 0.023~0.051 £gmol/g. Furthermore, experimental results indicated that TiO2 gave the highest average photo energy efficiency (AEf) of ~4.13%, and apparent quantum efficiency (£pA) of ~1.05%. However, the ZrO2 gave the highest average photo energy efficiency (AEf) of 5.07¡Ñ10-3%, and apparent quantum efficiency (£pA) of ~1.54¡Ñ10-2%.

Acrylic resins, synthesized from a mixture of monomers selected from the methacrylate, acrylate and styrene families, are the base polymer components for many automotive coatings due to their excellent chemical and mechanical properties. The low molecular weight polymers with reactive functionalities are made via high-temperature starved-feed free-radical solution semibatch terpolymerization, operating conditions that greatly promote the importance of secondary reactions, such as methacrylate depropagation, and acrylate backbiting, chain scission and macromonomer propagation. In this work, a generalized model for styrene/methacrylate/acrylate terpolymerization has been developed and formulated in the PREDICI software package and poorly understood high temperature mechanisms have been studied. Unknown rate coefficients for methacrylate depropagation, reactivity of acrylate macromonomer and penultimate copolymerization kinetics were determined via separate kinetic experiments. The generality of the terpolymerization mechanistic model was verified against data obtained under a range of polymerization conditions, and provides an exclusive insight into the kinetic complexity of methacrylate/styrene/acrylate terpolymerization at high temperatures. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-04-28 19:56:36.906

The use of hydroxyl radical based reaction (Fenton reaction) for the destruction of organic pollutants has been widely reported in the literature. However, the low pH requirement and rapid hydrogen peroxide consumption rate make the application of conventional Fenton reaction difficult for in-situ treatment. In this study, we conducted a modified Fenton reaction by introducing a chelating agent into the reaction system that could prevent Fe(OH)3 (s) precipitation even at a neutral pH condition and reduce the H2O2 consumption rate by controlling the Fe2+ concentration. A chelating agent (mono-chelate or poly-chelate) combines with Fe2+ or Fe3+ to form stable metal-chelate complexes in solution. This decreases the concentration of Fe2+ in the solution so that reactions can be carried for longer contact times. Experimental results (citrate was the chelating agent) for 2,4,6-trichlorophenol (TCP) showed that TCP degradations were greater than 95% after 2.5 h and 24 h reaction times at fixed pH 5 and 6, respectively. For the same reaction time, the normalized chloride formations were 85% at pH 5 and 88% at pH 6. Several other chlorinated organic compounds were also chosen as the model compounds for detoxification studies because of their chemical structures: trichloroethylene (unsaturated hydrocarbon), carbon tetrachloride (highly oxidized compound), 2,2-dichlorobiphenyl, and biphenyl (a dual-aromatic ring structure). Poly-chelating agents (such as polyacrylic acid-PAA) provide multiple Fe2+/Fe3+ binding sites in the modified Fenton reaction for the oxidation of contaminants (2,2-dichlorobiphenyl, and biphenyl) at a neutral pH environment. Numerical simulation based on the kinetic model developed from the well known Fenton reaction and iron-chelate chemistry fits experiment data well for both standard and chelate modified Fenton reactions. In this dissertation, it was proven that both monomeric (citrate) and polymeric (PAA) chelate modified Fenton reactions were effective for dechlorination of carbon tetrachloride from aqueous phase by the superoxide radical anion. On the other hand, PAA (a poly-chelating agent) can also be used for solid surface modification by polymerization of acrylic acid (monomer). The successful degradations of biphenyl and trichloroethylene by the PAA functionalized silica particles/membrane demonstrate the versatile applications of the chelate modified Fenton reaction.

The road transportation is a big source for the release of NOx emissions. NOx has been confirmed to cause negative affect on the air-quality especially in the urban areas, there are therefore regulations for allowed released amount from vehicles. The most adopted technology used for the reduction of these NOx emissions from the diesel exhaust gas is the ammonium selective catalytic reduction (NH3-SCR) using a Cu-zeolite as the catalyst in the system. The SCR catalyst can be deactivated through different mechanism, whereas poisoning by sulfur has been documented to be an important factor for the deactivation. The degree of deactivation of the catalyst has been suggested to vary depending on the catalytic material and which sulfur conditions the catalyst is exposed to, where SO3 has been indicated to cause more sever deactivation compared to SO2.  The aim of this project has been to investigate the deactivation mechanism of Cu-zeolites at different SOx conditions and evaluate potential regeneration mechanism. The project was carried out by evaluating the catalysts, Cu-BEA and Cu-SSZ-13, over different reactions that occurs in the SCR system, investigating the deactivation effect caused by SO2 poisoning and the regeneration potential. The project was then continued with the focus on the Cu-SSZ-13 catalyst investigating different SOx poisoning and regeneration conditions were investigated. In order to investigate the SO3 poisoning a generator using oxidation of SO2 to SO3 was successfully build during this project.  A kinetic model over the Cu-SSZ-13 NH3-SCR reactions was also built based on literature studies and the experimental data obtained. The results from the sulfur poisoning of Cu-BEA are based on the master thesis by Maria Arvanitidou. The fresh samples Cu-Beta and Cu-SSZ-13 exhibited similar activity, with the exception of the high formation of N2O observed over Cu-Beta under SCR conditions. The SO2 causes deactivation, especially at low temperatures. Cu-SSZ-13 exhibited more loss in activity but was able to recover more through the elevated SCR regeneration steps than the Cu-Beta. When SO2 exposure was performed together with NH3, larger deactivation was observed, likely due to ammonium sulfate species formed on the surface. The ammonium sulfate species were less thermally stable than copper sulfates, making it easier to recover the loss of activity in the Cu-SSZ-13. SO3 caused a much more sever deactivation of the SCR reactions than that of the SO2 poisoning and continued to show the lowest NOx removal activity after the regeneration process.  A difference in initial deactivation and recovery of activity between standard and fast SCR reactions was observed, indicating that the different mechanisms used are affected differently by the poisoning. The kinetic model for NH3-SCR over the Cu-SSZ-13 was successfully created when compared to the experimentally obtained data.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The piggery for many years was characterized as a waste-generating activity of high polluter, but in recent decades many studies are responsible for changing this concept. The use of biodigester is well disseminated to lessen the impacts generated by this activity, gaining encouragement deployment in recent years, by encouraging the use of renewable energy. The biodigester is responsible for the production of biogas used as alternative energy on farms that have the digesters system. We observed few studies that investigate the geometry of the digesters and its effects on anaerobic digestion process. This work aimed to study the partitioning of the Canadian model digester anaerobic digestion of swine waste applied to evaluating the degradation (removal) of the physic-chemical parameters (temperature, pH, COD, BOD5, total nitrogen, total phosphorus, total solids, total fixed solids and total volatile solids), and determining a kinetic model describing the biogas produced in each of the compartments of the digesters. For the study were built three reactors in bench scale: the first with a partitioning which caused variation of the horizontal flow, the second with partitioning which flux change generated in the vertical and third, without fragmentation, to be used as a reactor testimony. The analyzes of the physicchemical parameters were made according to Standard Methods for the Examination of Water and Wastewater, since the determination of the kinetic model was done considering the existence of a plug flow (tubular reactor) to each of the reactors constructed and to qualification of biogas was use a gas chromatograph. On the analysis of physic-chemical was second reactor (flow variation vertically) that showed that showed a significant difference in the efficiency of COD removal and pH values, and this reactor also showed better removal of solids and BOD5. Already temperature, showed similar behavior in the three reactors, characterizing the anaerobic digestion occurred primarily in the mesophilic range. Considering the BOD5 as a substrate was obtained as rate constant 0.021 d-1, 0.025 d-1 and 0.024 d-1, respectively for the first, second and third reactor. However, considering the COD as a substrate was obtained 0.032 d-1, and 0.034 d-1, 0.027 d-1 for each of the reactors. Kinetic models had a higher correlation with the experimental data when considering the COD as substrate, and was the second reactor with the highest correlation (R2 = 0.599). In the evaluation of biogas the three reactors not showed difference between them. / A atividade suinícola por muitos anos foi caracterizada como uma atividade geradora de resíduos de alto índice poluidor, porém nas últimas décadas muitos são os estudos responsáveis por mudar esse conceito. O uso de biodigestor está bem disseminado para diminuir os impactos gerados por essa atividade, ganhando estímulo de implantação nos últimos anos, pelo incentivo ao uso de energia renovável. O biodigestor é responsável pela produção do biogás, usado como energia alternativa em propriedades rurais que possuem o sistema de biodigestores. Observam-se poucos trabalhos que pesquisam a geometria dos biodigestores e seus efeitos no processo de digestão anaeróbia. Esse trabalho objetivou o estudo da compartimentação do biodigestor modelo canadense no processo de digestão anaeróbia aplicada a resíduos da suinocultura, avaliando a degradação (remoção) dos parâmetros físico-químicos (temperatura, pH, DQO, DBO5, Nitrogênio total, Fósforo total, sólidos totais, sólidos fixos totais e sólidos voláteis totais), determinando um modelo cinético e qualificando o biogás produzido em cada um dos compartimentos dos biodigestores. Para o estudo foram construídos três reatores em escala de bancada: o primeiro com uma compartimentação que provocava variação de fluxo na horizontal, o segundo com uma compartimentação, a qual gerava variação de fluxo na vertical e o terceiro, sem compartimentação, para ser utilizado como um reator testemunho. As análises dos parâmetros físicoquímicos foram realizadas de acordo com o Standard Methods for Examination of Water and Wastewater, já a determinação do modelo cinético foi realizada considerando a existência de um fluxo pistão (reator tubular) para cada um dos reatores construídos e para a qualificação do biogás utilizou-se um cromatógrafo a gás. Quanto à avaliação dos parâmetros físico químicos, foi o segundo reator (variação de fluxo na vertical) que apresentou diferença significativa na eficiência de remoção de DQO e nos valores de pH, sendo que esse reator também apresentou melhor remoção de DBO5 e sólidos. A temperatura apresentou comportamento semelhante nos três reatores, caracterizando que a digestão anaeróbia ocorreu prioritariamente na faixa mesofílica. Considerando a DBO5 como substrato obteve-se como constante de velocidade 0,021 d-1; 0,025 d-1 e 0,024 d-1, respectivamente para o primeiro, segundo e terceiro reator. Todavia, considerando a DQO como substrato obteve-se 0,032 d-1; 0,034 d-1 e 0,027 d-1 para cada um dos reatores. Os modelos cinéticos apresentaram uma maior correlação com os dados experimentais quando considerada a DQO como substrato, sendo que foi o segundo reator que apresentou maior correlação (R2 = 0,599). Na avaliação do biogás os três reatores não apresentaram diferença entre si.

A pesquisa propôs avaliar o desempenho e o comportamento de reatores seqüenciais em batelada com biomassa suspensa e imobilizada, em escala de bancada, na remoção de compostos de nitrogênio. Tais sistemas foram testados como tratamento complementar de reatores sulfetogênico e metanogênico utilizados no tratamento de água residuária industrial com alta concentração de sulfato e amônia. Visou o desenvolvimento de uma estratégia de operação que viabilizasse o uso dos próprios constituintes da água residuária para a maximização da eficiência do tratamento. O estudo foi dividido em 3 etapas principais. Na etapa 1 (181 dias de operação), o reator com biomassa suspensa foi mantido com 4 fases alternadas aeróbio/anóxico e ciclo de 24 horas, e verificou-se a presença da desnitrificação endógena (eficiência de remoção de nitrogênio de 65 \'+ OU -\' 27%). Para a etapa 2 (127 dias de operação), o reator de biomassa suspensa foi submetido ao tempo de ciclo de 12 horas, com uma fase aeróbia (6 horas) e com posterior fase anóxica (6 horas). Nessa etapa adicionou-se efluentes dos reatores metanogênico e sulfetogênico, ricos em ácidos voláteis (ácido acético), com intuito de acelerar o processo desnitrificante. Os resultados obtidos foram baixos em termos de remoção de nitrogênio (42 \'+ OU -\' 21%). Para a etapa 3 (134 dias de operação), foram ensaiados vários meios suportes, através de técnica de microsensores de oxigênio dissolvido, a fim de verificar a formação de biofilme específico (nitrificante/desnitrificante) e optou-se pelo uso do carvão mineral no reator com biomassa imobilizada. Nesta última etapa, foi mantida a estratégia operacional adotada na etapa 2 (ciclo 12 horas), bem como a adição de parcela do afluente na fase anóxica. A remoção de nitrogênio, com períodos aeróbio e anóxico e ciclo de 12 horas, mostrou-se viável no reator com biomassa imobilizada (eficiência de remoção de nitrogênio de 72 \'+ OU -\' 13%). Ao final dos ensaios experimentais, realizaram-se modelagens cinéticas que permitiram a compreensão dos processos convencionais e não convencionais ocorridos nas várias etapas para remoção de nitrogênio, tais como desnitrificação em fase aeróbia e o processo ANAMMOX. / The purpose of this research was to evaluate the performance and the behavior of sequential batch reactors with suspended and immobilized biomass, in benches scale, for the nitrogen composite removal. Such systems had been tested as sulphetogenic and methanogenic reactors complementary treatment, used in an industrial waste water treatment with high sulphate and ammonia concentrations. The research aimed for the development of an operation strategy that could make possible the use of the proper waste water constituent for the improvement of the treatment efficiency. The study was divided into 3 main stages. In stage 1 (181 days of operation), the reactor with suspended biomass was kept with 4 alternating phases aerobic/anoxic and a 24-hour cycle was used, and the endogenous denitrification was verified (nitrogen removal efficiency of 65 \'+ OU -\' 27%). For stage 2 (127 days of operation), the suspended biomass reactor was submitted to a cycle of 12 hours, with an aerobic phase (6 hours) and posterior anoxic phase (6 hours). In this stage effluent of the methanogenic and sulphetogenic reactors, rich in volatile acid (acetic acid), was added to accelerate the denitrify process. The achieved results had been low in terms of nitrogen removal(42 \'+ OU -\' 21%). For stage 3 (134 days of operation), some supports media was tested through dissolved oxygen microsensors technique, in order to check the specific biofilm formation (nitrificant/denitrificant) and the mineral coal was opted to be used in the immobilized biomass reactor. In this last stage it was adopted an operational strategy similar in stage 2 (12 hours cycle), as well as the addition of part of the affluent in the anoxic phase. The nitrogen removal, with aerobic and anoxic periods and 12 hours cycle, revealed feasible in the reactor with immobilized biomass (nitrogen removal efficiency of 72 \'+ OU -\' 13%). In the end of the experimental tests, kinetic modelings were done and had allowed the understanding of conventional and not conventional processes occurred in the stages for nitrogen removal, such as desnitrification in aerobic phase and ANAMMOX process.

This research investigated life cycle environmental impacts and benefits of an integrated microalgae system with wastewater treatment system using an integrated process modeling approach combined with experimentation. The overall goal of this research is to understand energy, carbon and nutrient balances in the integrated system and to evaluate the environmental impacts and benefits of the integrated system from a carbon, nutrient, and energy perspective. In this study, four major research tasks were designed to contribute to a comprehensive understanding of the environmental and economic sustainability of the integrated system, which included development of an integrated co-limitation kinetic model for microalgae growth (Chapter 2), kinetic parameter estimation models for anaerobic co-digestion (Chapter 3), development of an integrated process model (Chapter 4), and life cycle environmental and economic assessments of the integrated system (Chapter 5). The integrated co-limitation kinetic model was developed to understand microalgae growth in the centrate from dewatering of anaerobically digested sludge. This growth kinetic model considered four major growth factors, including Nitrogen (N), dissolved carbon dioxide (CO2) concentrations, light intensity, and temperature. The model framework was constructed by combining threshold and multiplicative structures to explain co-limitation among these factors. The model was calibrated and validated using batch studies with anaerobically digested municipal sludge centrate as wastewater source, and the model was shown to have a reasonable growth rate predictor for Chlorella sp. under different nutrient levels of the centrate. Anaerobic co-digestion was used for energy conversion process in the integrated system. To estimate methane production of anaerobic co-digestion, kinetic models commonly applied. To apply the kinetic model, determining kinetic parameters for anaerobic co-digestion of microalgae and waste activated sludge (WAS) is essential, and this research introduced two potential regression-based parameter estimation models to estimate the kinetic parameters. Using the estimation models presented, the kinetic parameters for co-digestion was able to be determined for different ratios of co-substrates with limited experiments. In this research, the integrated process model was developed to simulate the dynamic behavior of the integrated system. The model included the microalgae cultivation, harvesting, and anaerobic co-digestion processes in the integrated system to provide a comprehensive understanding of the integrated system. For cultivation, the integrated co-limitation kinetic model was applied to estimate microalgae productivity, while the regression-based parameter estimation model was used to determine the first order kinetic parameter to estimate methane production rates for anaerobic co-digestion. The simulated microalgae productivity results were comparable to typical microalgae productivity in open pond systems. For the integrated system, removal of NH4-N by microalgae was not efficient. In particular, the NH4-N removal was minimal during the winter season due to low microalgae growth. As the microalgae productivity increased, the CH4 and biosolids production increased as a result of the increased amount of the substrates from the harvested microalgae biomass. The increase of CH4 and biosolids productions, however, was minor because of the small amount of microalgae biomass for the co-digestion. Based on simulated data for integrated process modeling, the life cycle environmental and economic impacts of the integrated system (with different CO2 supply areas) were evaluated and compared to the conventional wastewater treatment system. The integrated systems had a lower carbon footprint, cumulative energy demand, and life cycle cost than the conventional system. The integrated system with 10% CO2 sparging area was able to achieve the lowest carbon footprint. Without CO2 addition during microalgae cultivation, the integrated system had the lowest energy balance and life cycle cost. However, there is no significant difference between the integrated and conventional systems for eutrophication potential because these systems had the same effluent quality. In terms of an energy saving with the integrated systems, the benefit of energy reduction for the wastewater treatment was greater than the energy production from the anaerobic co-digestion, compared to the conventional system. Overall, the integrated system can improve the carbon balance by reducing the life cycle energy required in the conventional system.