Cette thèse a été réalisée dans le cadre de la valorisation des composés organiques volatils (COVs) tels que le toluène. Cette étude vise à mettre au point des catalyseurs efficaces pour l'élimination du toluène par reformage à sec et vaporeformage du toluène. Les solides de type hydrotalcite ont été choisis en raison des propriétés intéressantes des oxydes obtenus par leur calcination. Les catalyseurs à base de Ni, Mg, et Al ont été préparés par voie hydrotalcite. Afin d'améliorer l'activité catalytique, les éléments Ce et La ont été incorporés dans les solides pour substituer une partie de l'élément Al et les effets ont été étudiés. Dans un premier temps, les différents oxydes mixtes ont été caractérisés par différentes techniques physico-chimiques dont la Diffraction des Rayons X (DRX), les Analyses Thermiques (ATD, ATG), la Réduction en Température Programmée (RTP),... Dans un deuxième temps, les différents oxydes mixtes ainsi préparés ont été testés dans les réactions de reformage à sec du toluène. La substitution progressive des ions Mg²⁺ par les ions Ni²⁺ améliore l'activité des catalyseurs. Le cérium ou le lanthane interviennent au niveau du mécanisme réactionnel pour améliorer la sélectivité tout en réduisant le dépôt de carbone. Les performances catalytiques des oxydes sont ensuite testées vis-à-vis de la réaction de vaporeformage du toluène montrant que la réactivité s'améliore avec l'augmentation de la teneur en magnésium. Les promoteurs ont montré un effet sur la conversion et la sélectivité en hydrogène. Selon les caractérisations physico-chimique après test catalytique, les catalyseurs n'ont montré aucune formation de coke. Une comparaison entre le meilleur catalyseur de cette étude et un catalyseur industriel est abordée. / This thesis was carried out in the context of the valorization of volatile organic compounds (VOCs) such as toluene. This study aimed to optimize efficient catalysts for the elimination of toluene by dry and steam reforming of toluene. Hydrotalcite solids were chosen because of the interesting properties of the oxides obtained by their calcination. The Ni, Mg and Al-based catalysts were prepared via hydrotalcite road. In order to improve the catalytic activity, the elements Ce and La were incorporated into the solids to substitute a part of the element A1 and the effects were studied. Initially, the mixed oxides were characterized by different physico-chemical techniques including X-Ray Diffraction, Thermal Analysis (TG/DTA), Temperature Programmed Reduction (TPR),... In a second step, the mixed oxides were tested in the dry reforming of toluene reaction. The progressive substitution of Mg²⁺ ions by Ni²⁺ ions improves the activity of the catalysts. Cerium or lanthanum played a role in the reaction mechanism, to improve selectivity and reduce carbon deposition. The catalytic performances of the oxydes are tested in the steam reforming of toluene reaction, showing that the reactivity improves with the increase in the magnesium content. The promoters have enhanced the toluene conversion and hydrogen selectivity. According to the physico-chemical characterizations after the catalytic test, the catalysts showed no coke formation. A comparison between the best catalyst of this study and an industrial catalyst is performed.

A new process is being developed to produce graphite from prime coking coal. Coal is dissolved in dimethylformamide (DMF), on addition of sodium hydroxide. The minerals and undissolved coal are separated by centrifugation and filtration to give a solution (referred to as Refcoal solution or RCS). Over 90 wt % of the organic part of a flotation product, from the Tshikondeni mine, can be dissolved at temperatures ranging from room temperature to 135°C. The purified coal (referred to as Refcoal) and DMF need to be separated. the Refcoal to be coked and the DMF to be purified and recycled. This process should be as efficient as possible, whilst both products should be low in water content to minimise drying costs. The addition of water to the Refcoal solution causes precipitation to take place, forming a gel (referred to as Refcoal gel) liquid system. This mixture can be either centrifuged or filtered to give a denser gel, containing water, DMF and coal solids, and supernatant or filtrate, containing water and DMF. Different techniques and processes can be used to improve the separation of the DMF from the Refcoal by achieving a denser Refcoal gel: • Longer centrifugation times improve the density and therefore the separation, but this technique has its limits. • The use of low-temperature water improves the separation. • The use of syneresis could improve separation at a lower cost: heated standing tanks are used to expel the supernatant and therefore increase the density of the gel, thereby decreasing the required number of washing stages. • The addition of toluene at the beginning of a wash improved the removal of DMF by 20%, using centrifugation as separation method. • Pressure filtration gave a 20% improvement on centrifugation, with no additives. • The addition of toluene to the pressure filtration process gave another improvement of 15%, and after three stages the percentage of solids in the gel was 28%, the highest so far achieved. This method also resulted in the highest removal of DMF in the first stage (73% of the original DMF in the RCS was removed). Counter-current washing shows the greatest potential, using the least amount of water. The concentration of DMF in the wash solution, to gel the Refcoal solution, is a limitation of this process. If the concentration is too high, no gelling and therefore no separation can take place in the first stage. It is recommended that counter-current washing using pressure filtration should be investigated; however, this will be difficult on a laboratory scale due to the mass losses during transfers. / Dissertation (MEng (Chemical Engineering))--University of Pretoria, 2009. / Chemical Engineering / unrestricted

Submitted by Adriana Martinez (amartinez@unoeste.br) on 2018-05-21T16:53:33Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Kátia.pdf: 1082341 bytes, checksum: bf243e25171e37a60f802300dab1ff02 (MD5) / Made available in DSpace on 2018-05-21T16:53:33Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Kátia.pdf: 1082341 bytes, checksum: bf243e25171e37a60f802300dab1ff02 (MD5) Previous issue date: 2018-03-21 / Leaks at gas stations cause major problems for the environment, especially with regard to contamination of groundwater and soils. The major problems of oil derivative contamination are attributed to monoaromatic hydrocarbons (BTEX - benzene, toluene and xylene), which are the most soluble and mobile constituents of the gasoline fraction, being the first to reach the water table. In the most recent survey carried out by the State Company of Environmental Sanitation Technology of the State of São Paulo (CETESB), it was identified that more than 85% of the contamination cases in the region of West Paulista are related to waste from fuel stations. The present study evaluated the toxicological potential of exposure of adult male rats to the commercial gasoline / ethanol blend (75/25 by volume), with emphasis on the possible impacts on reproductive morphophysiology. Adult male Wistar rats were allocated into 4 experimental groups (n = 8 / group). The animals received commercial gasoline diluted in corn oil via gavage at doses of 0 (control group- C), 16 (group A - GA), 160 (group B - GB) or 800 mg / kg / day (group C - GC). The reproductive organs were collected and weighed. The sperm parameters evaluated were motility, plasma membrane integrity and acrosomal, mitochondrial activity and morphology. In addition, the epididymis and right testis were collected for sperm counts. Histopathological analysis of the testis and epididymis, spermatogenesis and cell counts. For the machine learning test, different pattern recognition algorithms were used: Artificial Neural Network (ANN), Bayes Classifier (BAY), K-Nearest Neighbors (KNN), Support Vector Machine (SVM) and Optimum Path Forest OPF). The results were compared by ANOVA with Tukey's posterior test, and the Kruskall-Wallis test with Dunn's a posteriori, considering p <0.05. The sperm parameters were reduced in a dose-dependent manner. Mitochondrial activity and acrosomal integrity were decreased in the GC and GB groups in relation to the control group. There was an increase of isolated heads in the GC and GB groups in relation to the control group. Plasma membrane integrity was reduced in GC in relation to the control group. A decrease in the number of mobile spermatozoa with progressive trajectory was observed in the GC and GB groups, in relation to the control group. The daily sperm production was reduced in GC and GB in relation to the control group. In addition, this parameter was lower in GC than in GB. There was a significant delay in transit time in the tail of the epididymis in the GC and GB groups in relation to the control group. The number of Sertoli cells decreased in the GB and GC groups when compared to the CG and GB groups. Histopathological analysis, spermatogenesis and germ cell counts showed no significant difference between the groups. There was presence of pattern with the subdivision of two classes (control group and exposed groups), with better classification with the SVM test and 90% accuracy for control group. Thus, it was concluded that the exposure of rats to different doses of the commercial gasoline / ethanol mixture can alter spermatogenesis and sperm quality, with a recognizable classification pattern of machine learning algorithms. / Vazamentos em postos de combustíveis provocam grandes problemas ao meio ambiente, principalmente no que diz respeito à contaminação de águas subterrâneas e solos. Os maiores problemas da contaminação por derivados de petróleo são atribuídos aos hidrocarbonetos monoaromáticos (BTEX - benzeno, tolueno e xileno), que são os constituintes mais solúveis e mais móveis da fração da gasolina, sendo os primeiros a atingir o lençol freático. No mais recente levantamento realizado pela Companhia Estadual de Tecnologia de Saneamento Ambiental do Estado de São Paulo (CETESB), identificou-se que mais de 85% dos casos de contaminação na região do Oeste Paulista estão relacionados a resíduos de postos de combustíveis. O presente estudo avaliou o potencial toxicológico da exposição de ratos machos adultos à mistura comercial de gasolina/etanol (75/25 em volume), com ênfase nos possíveis impactos sobre a morfofisiologia reprodutiva. Ratos machos Wistar adultos foram alocados em 4 grupos experimentais (n=8/grupo). Os animais receberam gasolina comercial diluída em óleo de milho, via gavagem, nas doses de 0 (grupo controle - C), 16 (grupo A - GA), 160 (grupo B - GB) ou 800 mg/kg/dia (grupo C - GC). Os órgãos reprodutivos foram coletados e pesados. Os parâmetros espermáticos avaliados foram motilidade, integridade da membrana plasmática e acrossomal, atividade mitocondrial e morfologia. Além disso, o epidídimo e testículo direito foram coletados para contagens espermáticas. Também foram realizadas análise histopatológica do testículo e epidídimo, contagens dos estágios da espermatogênese e de células. Para o teste de aprendizado de máquina foram utilizados diferentes algoritmos de reconhecimento de padrões: Artificial Neural Network (ANN), Bayes Classifier (BAY), K-Nearest Neighbors (K-NN), Support Vector Machine (SVM) e Optimum Path Forest (OPF). Os resultados foram comparados por ANOVA com o teste “a posteriori” de Tukey, e o teste de Kruskall-Wallis, com “a posteriori” de Dunn, considerando p<0,05. Os parâmetros espermáticos foram reduzidos de maneira dose-dependente. A atividade mitocondrial e integridade acrossomal foram diminuídas nos grupos GC e GB em relação ao grupo controle. Houve um aumento de cabeças isoladas nos grupos GC e GB em relação ao grupo controle. A integridade de membrana plasmática foi reduzida em GC em relação ao grupo controle. Foi observada uma redução no número de espermatozoides móveis com trajetória progressiva nos grupos GC e GB, em relação ao grupo controle. A produção diária espermática foi reduzida em GC e GB em relação ao grupo controle. Além disso, este parâmetro foi menor em GC em relação a GB. Houve um atraso significativo no tempo de trânsito na cauda do epidídimo nos grupos GC e GB em relação ao grupo controle. O número de células de Sertoli sofreu redução nos grupos GC e GB quando comparado aos grupos controle e GA. A análise histopatológica, contagem dos estágios da espermatogênese e de celulas germinativas não apresentaram diferença significativa entre os grupos. Houve presença de padrão com a subdivisão de duas classes (grupo controle e grupos expostos), com melhor classificação com o teste SVM e 90% de acurácia para o grupo controle. Assim, concluiu-se que a exposição de ratos a diferentes doses da mistura comercial de gasolina/etanol pode alterar a espermatogênese e a qualidade espermática, com reconhecível padrão de classificação de algoritmos de aprendizado de máquina.

[pt] Neste estudo foi avaliada a capacidade de adsorção do poluente orgânico tolueno em contato com a cepa Rhodococcus opacus. O tolueno foi selecionando por fazer parte do grupo de compostos BTEX (Benzeno, Tolueno, Etilbenzeno e Xileno), que possui elevada toxicidade, causando impacto ambiental em corpos hídricos, solo e ar, além de possuir características mutagênica e carcinogênica em humanos. A determinação e quantificação do tolueno na solução aquosa foram realizadas em um cromatógrafo a gás, acoplado ao espectrômetro de massas com amostrador automático headspace. A cepa Rhodococcus opacus foi caracterizada por análise de espectrometria no infravermelho e medição de potencial zeta, sendo a última realizada antes e após o contato com o tolueno. Os modelos de isotermas lineares de Langmuir, Freundlich e Temkin foram aplicados aos dados experimentais para descrever o processo de adsorção. Tendo o modelo de Langmuir se adaptado melhor ao processo em análise. As variáveis estudadas para otimizar as condições máximas de adsorção foram: tempo de contato, variação do pH, variação da biomassa. Este estudo mostrou que a cepa bacteriana R. opacus apresentou uma boa capacidade de biossorção, principalmente para concentrações baixas, onde removeu 95,99 porcento e 85,69 porcento das respectivas concentrações de 0,6 e 0,8 mg/L de tolueno, atendendo a resolução do CONAMA 357/2005 para águas salobras de Classe I. / [en] In this study was evaluated the adsorption capacity of the organic pollutant toluene by the Rhodococcus opacus strain. Toluene was chosen by being part of the group of BTEX compounds (benzene, toluene, ethylbenzene and xylene), which has high toxicity, causing environmental impact on water bodies, soil and air, and also are mutagenic and carcinogenic to humans. The determination and quantification of toluene in aqueous solution were performed on a gas chromatograph, coupled with a mass spectrometer with headspace autosampler. The strain Rhodococcus opacus was characterized by infrared spectrometry analysis and zeta potential measurement, the last done before and after the sorption. The isotherm linear models of Langmuir, Freundlich and Temkin were applied to the experimental data to describe the adsorption process. Having the Langmuir model better adapted to process analysed. The variables studied to optimize the maximum adsorption conditions were: contact time, pH variation, biomass variation. This study showed that the bacterial strain R. opacus has good biosorption capabilities, particularly at low concentrations, where it removed 95.99 percent and 85.69 percent of the respective concentrations of 0.6 and 0.8 mg/L of toluene, attending the CONAMA resolution 357/2005 for salt waters of Class I.

Neutron detection is important in several fields, especially detection of illicit nuclear material. Historically, 3He has been the basis for these technologies. Modern realities have necessitated the development of new technologies and the exploration of new materials to meet this need. One potential solution is known as capture-gating, which is a measurement approach that is good at differentiating between incident neutrons and gamma rays. The key issue is that materials used in current capture-gating devices can suffer from poor optical performance. This is due to the fact that the these detectors, whether composed of a heterogeneous or homogeneous mixture of materials, are made of dissimilar materials. In the homogeneous case, this frequently results in a cloudy material (e.g. lithium-gadolinium-borate crystals), while heterogeneous cases suffer from index mismatch (e.g. glass inside a plastic scintillator). The goal of this thesis is material development and processing toward an index-matched, gadolinium-based glass, heterogeneous capture-gated neutron detector. This involved identifying the refractive index range of known gadolinium glasses and the development of polystyrene (PS) and polyvinyl toluene (PVT) co-polymers with a range of refractive indices. Specifically 1:3, 1:1, and 3:1 PS:PVT ratios were manufactured and their refractive indices were compared to those of pure PS and PVT. Two methods for uniform glass dispersion were explored; the use of a rotisserie oven and the use of centrifugal planetary mixer. Ellipsometry, refractometry, and spectroscopic transmission were all performed to optically evaluate the manufactured polymers and polymer/glass composites. The ability to produce a PS/PVT copolymer with a refractive index in the range of known gadolinium glasses was demonstrated. In addition, the benefit of matching the refractive indices when producing a glass/polymer composite was explored and the effect of index mismatch was observed. The ability to predict the refractive index of a PS/PVT blend was demonstrated but can still be improved upon. While a novel index-matched gadolinium-based heterogeneous capture-gated neutron detector was not developed as part of this work, progress was made on all material aspects to further develop a detector meeting that description. More work still needs to be done in fine tuning the index match of the glass and polymer components, in determining the ideal method of glass dispersion, and in producing larger samples.

The facultative denitrifying alphaproteobacterium Magnetospirillum sp. strain 15-1 had been isolated from the hypoxic rhizosphere of a constructed wetland model fed with toluene. This bacterium can catabolize toluene anaerobically but not aerobically. Here, we used strain 15-1 to investigate regulation of expression of the highly oxygen-sensitive glycyl radical enzyme benzylsuccinate synthase, which catalyzes the first step in anaerobic toluene degradation. In cells growing aerobically with benzoate, the addition of toluene resulted in a ~20-fold increased transcription of bssA, encoding for the catalytically active subunit of the enzyme. Under anoxic conditions, bssA mRNA copy numbers were up to 129-fold higher in cells growing with toluene as compared to cells growing with benzoate. Proteomics showed that abundance of benzylsuccinate synthase increased in cells growing anaerobically with toluene. In contrast, peptides of this enzyme were never detected in oxic conditions. These findings show that synthesis of benzylsuccinate synthase was under stringent post-transcriptional control in the presence of oxygen, which is a novel level of regulation for glycyl radical enzymes.

The sulfonation of toluene at -12.5° C. with sulfur trioxide in liquid sulfur dioxide was found to give 10.03 ± 0.20 % ortho, 0.73 ± 0.20 % meta and 89.24 ± 0.20 % para isomers. This isomer distribution was determined by isotope dilution analysis using sulfur-35 enriched sulfur trioxide. After dilution of aliquots of the neutralized sulfonation mixture with pure sodium salts of each of the isomers prepared from the corresponding toluidines, the isomers were converted to the p-toluidine salts, purified by recrystallization, and counted by liquid scintillation counting. The relative rate of sulfonation of toluene compared to benzene was studied under the same conditions. The analysis in this case was accomplished by ultraviolet spectrophotometry. The only assumption made was that the isomer distribution of toluene does not change when benzene is added during the sulfonation. The results show that the relative rate (kt/kb) is 10.9 ± 1,5 at low benzene to toluene ratios but increases considerably at high ratios. The hydrochlorination of cyclohexerte, cis-2-butene and trans-2-butene with stannic chloride catalyst was studied in n-heptane solvent. The kinetics were found to be considerably influenced by trace impurities, especially moisture. The kinetics were found to be first order in olefin and stannic chloride and from zero to three and one-half order in hydrogen chloride depending on the amount of moisture present. When moisture is absent, unexplained abnormal kinetics occurred. Polymerization, cyclization, alkylation, and dehydrochlorination were insignificant under the conditions of the kinetic experiments.

No description available.

No description available.

Commercially important hydrogenation reactions make use of precious noble metal catalysts which are becoming increasingly scarce, and the search for capable alternative catalysts prevails. Transition metal carbides of group IV-VI metals show similar catalytic behavior to platinum and are $103/kg lower in price than the precious metal catalysts. Tungsten carbide, studied in this work, can form in different stoichiometries and phase compositions depending upon synthesis methods. Synthesis of high surface area tungsten carbide with control over its phase composition remains a challenge currently. In this work, the novel isothermal synthesis method of tungsten carbide (WC, W2C) in a CH4/H2 carburization atmosphere with synthesis temperature and presence or absence of a silica support in the catalyst precursor (WO3) as process variables was investigated. The amounts of CO and H2O formed during synthesis corresponded to the amount of oxygen in the WO3 precursor. The catalysts were further characterized by X-ray diffraction to determine phase composition and crystallite size, by scanning electron microscopy to determine morphology, and by CO chemisorption to determine metallic surface area. X-ray diffraction analysis indicated the carbide catalysts to contain W2C, WC, and metallic W phases. The use of a silica-supported precursor favored the formation of a nearly phase pure, high surface area W2C rich catalyst whereas high synthesis temperature and absence of silica precursor favored formation of a low surface area WC rich catalyst. Further, the catalysts were tested for steady state activity at a W/F (weight catalyst/toluene feed rate) of 0.20-0.30 h-1, addition of H2 to a total pressure of 21 bar absolute and 250 °C, and the effect of phase composition and surface area on the activity was studied. This work resulted in the successful synthesis of 4 tungsten carbide catalysts with varying phase compositions and surface areas and correlation of their compositions and surface areas with their corresponding toluene hydrogenation activities.