O desenvolvimento industrial tem, como conseqüência, a maior geração de resíduos, muitos deles tóxicos aos seres vivos. Dentre esses, benzeno, tolueno e xilenos (BTX), derivados do petróleo, estão contaminando aqüíferos por acidentes no transporte e no armazenamento. Por esse motivo, diversas pesquisas têm sido realizadas buscando formas de biodegradar BTX. Esses trabalhos indicam que os principais fatores que podem influenciar a degradação biológica dos BTX são temperatura, pH, disponibilidade de nutrientes, concentração de tóxicos e diversidade de microrganismos. Visando contribuir com o estudo desses fatores, este trabalho teve por objetivo avaliar a influência do inóculo e de aceptores de elétrons no processo de degradação anaeróbia de BTX. Neste trabalho três inóculos foram pesquisados: 1- biomassa proveniente de reator anteriormente submetido à mistura de gasolina comercial e água; 2- biomassa proveniente de reator da estação de tratamento de esgoto da USP - São Carlos; 3- biomassa proveniente de reator tratando água residuária de abatedouro de aves. Os resultados obtidos comprovaram que a origem do inóculo foi fundamental na degradação anaeróbia de BTX, pois os inóculos apresentaram diferentes períodos de adaptação e porcentagens de degradação do tóxico. Depois de 93 dias de operação os inóculos 1, 2 e 3 apresentaram eficiência de remoção de BTX da ordem de 57%, 83% e 90%, respectivamente. O reator com o inóculo 3 foi submetido a condições metanogênica, sulfetogênica com presença e ausência de Ferro (III). Os resultados demonstraram que a degradação dos BTX foi influenciada pelas diferentes condições adotadas. A adição de Fe (III) melhorou a degradação dos BTX, do reator sob condições sulfetogênicas. / The industrial development has increased the generation of residues. Some of them are toxics and impact the environment. Benzene, toluene and xylenes (BTX), petroleum sub products, are examples of such toxic compounds. These compounds may contaminate aquifers as a result of accidents during transportation or of leakages of storage tanks. Several factors are reported to affect the biodegradation of BTX, such as: temperature, pH, availability of nutrients, concentration of toxics and diversity of microorganisms. This research aimed to study some of these factors, such as different inoculum sources and different electrons acceptors during BTX degradation processes in an horizontal-flow anaerobic immobilized biomass (HAIB) reactor. In this research three inocula were studied: 1- an adapted microbial community for BTX degradation; 2 - microorganisms collected from a pilot-scale UASB reactor treating domestic wastewater; and 3 - Microorganisms collected from an UASB treating poultry slaughterhouse industry wastewater. The results have shown that the inoculum sources were fundamental to the adaptation period for the toxic biodegradation, producing different BTX removal efficiencies. After 93 days of operation, the inocula 1, 2 and 3 showed BTX removal efficiency of 57, 83 and 90%, respectively. The inoculum 3 was submitted to conditions of methanogesis and sulfetogenesis in the presence and absence of Fe (III). The results demonstrated that BTX degradation was affected by the different conditions adopted, showing that the addition of Fe (III) improved biodegradation in the reactor under sulfate reduction condition.

L'hydrodynamique et les transferts thermiques dans des réacteurs types lits fixes font l'objet d'études depuis une soixantaine d'années. Les informations fournies par ces travaux sont importantes pour le dimensionnement des réacteurs industriels. En effet, une étroite relation entre les propriétés de transports et le design du procédé (réacteur et support catalytique) est mise en avant dans l'état de l'art. Mais force est de constater que la complexité des phénomènes entraine des divergences entre les observations et les différentes conclusions faites par les auteurs. Deux pilotes à échelle laboratoire ont été conçus et mis en place au cours de cette thèse. L'un est dédié à l'étude hydrodynamique et l'autre à l'étude thermique. La caractérisation hydro-thermique des réacteurs passe également par une étape de développement de modèles mathématiques associés aux pilotes. Ils représentent les transferts opérant au sein d'une colonne garnie. Ils permettent également d'estimer les paramètres effectifs du milieu poreux. Les quatre grandeurs caractéristiques étudiées dans cette thèse sont les pertes de charges, la dispersion axiale, la conductivité effective globale et le coefficient d'échange thermique à la paroi. Les résultats obtenus à partir des modèles sont comparés aux travaux de la littérature. Ceci permet de valider les méthodes d'estimation développées dans cette thèse. Il est remarqué que les corrélations prédictives de la conductivité effective sont peu adaptées aux morphologies de supports les plus complexes. Nous proposons donc aussi de nouvelles corrélations basées sur nos mesures / Hydrodynamics and heat transfers in packed bed reactors have been studied for about sixty years. The information supplied by this work is important for the design of industrial reactors. Indeed, there is a close relationship between the heat and mass transfers and the design of the process (reactor and catalytic support); this is highlighted in the state of the art. It is clear that the complexity of the phenomena is the cause of divergences between the observations and the conclusions made by the authors. Two laboratory-scale pilots were designed and set up during this PhD thesis. One is dedicated to the hydrodynamic studies and the other to the thermal studies. The hydro-thermal characterization of the reactors includes a step of development of mathematical models associated with the pilots. They represent transfers occurring within the bed of particles. Coupling experimental data with the models allows estimating the effective parameters of the porous medium. The four characteristic quantities studied in this PhD thesis are the pressure drop, the axial dispersion, the overall effective conductivity and the heat transfer coefficient at the wall. The results are compared with the data provided by the open literature. This validates the estimation methods developed during this PhD thesis. It is noticed that the predictive correlations of the effective thermal conductivity are not adapted to the morphologies of the most complex supports. Based on our measurements, new correlations were developed

Este trabalho teve como objetivo a produção de hidrogênio em reator anaeróbio de leito fixo com fluxo ascendente utilizando-se efluente de indústria de refrigerantes. Os resultados obtidos demonstraram que a água residuária semi-sintética simulando efluente de indústria de refrigerantes tem um bom potencial de geração de hidrogênio. Dados da operação dos dois reatores utilizados mostraram que o maior rendimento foi alcançado pelo reator operado sem a adição de meio contendo nutrientes (R2), pois este foi capaz de atingir 4,2 mol \'H IND.2\'/mol de substrato em contraste com 2,5 mol \'H IND.2\'/mol de substrato, obtida pelo reator (R1), cujo afluente continha suplementação nutricional. Constatou-se que o reator operado sem adição de nutrientes (R2) apresentou continuidade na produção de hidrogênio, fato que não ocorreu com o reator R1, que exibiu uma produção efêmera e significativamente inferior. O melhor desempenho na velocidade de produção de hidrogênio e porcentagem do mesmo na composição do biogás também foi observado para o reator R2, que atingiu 0,52 L/h.L e 18,9% de \'H IND.2\' contra 0,28 L/h.L e 2,1% de \'H IND.2\' obtidos pelo reator com suplementação nutricional (R1). Após esta primeira etapa comparativa em que os reatores foram operados simultaneamente com TDH teórico de 0,5 h, prosseguiu-se apenas com a operação do reator R2, porém com tempo de detenção hidráulica teórico de 1 h, o que induziu uma maior conversão do substrato a ácidos e álcoois, mudou as características hidrodinâmicas do leito e afetou negativamente a produção de hidrogênio. / This work was aimed on hydrogen production in an upflow anaerobic packed-bed reactor fed with soft-drink wastewater. The results obtained show that the semisynthetic soft-drink wastewater has a good hydrogen generation potential. Data obtained from the operation of both reactors indicated that the reactor operated without the addition of medium containing macro and micronutrients (R2) provided higher hydrogen yield (4,2 mol \'H IND.2\'/mol of substrate) as compared to the reactor (R1) operated with the addition of nutrient medium, which achieved lower hydrogen production yield (2,5 mol \'H IND.2\'/mol of substrate). It was observed that the reactor operated without the addition of nutrients (R2) showed continuous hydrogen production, while the reactor R1 exhibited a short period of production and lower amounts of hydrogen. Better hydrogen production rate and percentage in the biogas were also observed for the reactor R2, which achieved 0,52 L/h.L and 18,9% of \'H IND.2\' against 0,28 L/h.L and 2,1% of \'H IND.2\' obtained by the reactor with nutrient addition (R1). After operation with HDT of 0,5 h, the reactor R2 was operated with theoretical HDT of 1 h. Under this condition, the substrate was mainly converted to acids and solvents, negatively affecting the hydrogen production and the hydrodynamic pattern of the reactor.

O desenvolvimento industrial tem, como conseqüência, a maior geração de resíduos, muitos deles tóxicos aos seres vivos. Dentre esses, benzeno, tolueno e xilenos (BTX), derivados do petróleo, estão contaminando aqüíferos por acidentes no transporte e no armazenamento. Por esse motivo, diversas pesquisas têm sido realizadas buscando formas de biodegradar BTX. Esses trabalhos indicam que os principais fatores que podem influenciar a degradação biológica dos BTX são temperatura, pH, disponibilidade de nutrientes, concentração de tóxicos e diversidade de microrganismos. Visando contribuir com o estudo desses fatores, este trabalho teve por objetivo avaliar a influência do inóculo e de aceptores de elétrons no processo de degradação anaeróbia de BTX. Neste trabalho três inóculos foram pesquisados: 1- biomassa proveniente de reator anteriormente submetido à mistura de gasolina comercial e água; 2- biomassa proveniente de reator da estação de tratamento de esgoto da USP - São Carlos; 3- biomassa proveniente de reator tratando água residuária de abatedouro de aves. Os resultados obtidos comprovaram que a origem do inóculo foi fundamental na degradação anaeróbia de BTX, pois os inóculos apresentaram diferentes períodos de adaptação e porcentagens de degradação do tóxico. Depois de 93 dias de operação os inóculos 1, 2 e 3 apresentaram eficiência de remoção de BTX da ordem de 57%, 83% e 90%, respectivamente. O reator com o inóculo 3 foi submetido a condições metanogênica, sulfetogênica com presença e ausência de Ferro (III). Os resultados demonstraram que a degradação dos BTX foi influenciada pelas diferentes condições adotadas. A adição de Fe (III) melhorou a degradação dos BTX, do reator sob condições sulfetogênicas. / The industrial development has increased the generation of residues. Some of them are toxics and impact the environment. Benzene, toluene and xylenes (BTX), petroleum sub products, are examples of such toxic compounds. These compounds may contaminate aquifers as a result of accidents during transportation or of leakages of storage tanks. Several factors are reported to affect the biodegradation of BTX, such as: temperature, pH, availability of nutrients, concentration of toxics and diversity of microorganisms. This research aimed to study some of these factors, such as different inoculum sources and different electrons acceptors during BTX degradation processes in an horizontal-flow anaerobic immobilized biomass (HAIB) reactor. In this research three inocula were studied: 1- an adapted microbial community for BTX degradation; 2 - microorganisms collected from a pilot-scale UASB reactor treating domestic wastewater; and 3 - Microorganisms collected from an UASB treating poultry slaughterhouse industry wastewater. The results have shown that the inoculum sources were fundamental to the adaptation period for the toxic biodegradation, producing different BTX removal efficiencies. After 93 days of operation, the inocula 1, 2 and 3 showed BTX removal efficiency of 57, 83 and 90%, respectively. The inoculum 3 was submitted to conditions of methanogesis and sulfetogenesis in the presence and absence of Fe (III). The results demonstrated that BTX degradation was affected by the different conditions adopted, showing that the addition of Fe (III) improved biodegradation in the reactor under sulfate reduction condition.

科学研究費補助金 研究種目:一般研究(C) 課題番号:62550695 研究代表者:中村 正秋 研究期間:1987-1988年度

Cette étude a porté sur le développement de procédés continus performants de production d’esters à partir de l’huile de tournesol hautement oléique vierge ou raffinée en réacteurs enzymatiques à lit fixe, très productifs et stables dans le temps. Un procédé de transestérification continue en réacteur à lit fixe utilisant Novozyme 435 (lipase B de candida antarctica immobilisée sur Lewatit VP OC 1600), biocatalyseur non régio-spécifique, a été optimisé pour transformer de l’huile vierge de tournesol hautement oléique en esters butyliques. Les phénomènes de partition des composés polaires (phospholipides présents initialement dans l’huile, du glycérol co-produits etc.) entre milieu réactionnel et support enzymatique ont été gérés grâce à l’utilisation de tert-butanol, un solvant polaire. Les conditions assurant le meilleur compromis entre stabilité, productivité et rendements de production d’esters ont été obtenues pour une concentration initiale en huile de 500mM et un rapport molaire entre substrats de 5. De telles conditions permettent une productivité de 13,8 tonnes.an-1.kg de Novozyme 435-1. Le réacteur ainsi dimensionné s’est avéré stable pendant 50 jours consécutifs sans aucune perte d’activité, permettant de minimiser le coût élevé de l’enzyme. L’originalité du procédé est l’utilisation d’huiles vierges contenant des antioxydants naturels (phospholipides, tocophérols etc.). Nous avons démontré que ces composés mineurs sont préservés au cours du procédé de transestérification. Cela confère aux esters formés de remarquables propriétés de résistances à l’oxydation.La pertinence économique du procédé a été améliorée grâce au développement d’un nouveau biocatalyseur sur support hydrophobe (l’Accurel MP) permettant d’éviter toute adsorption de composés polaires. Une analyse économique du procédé (maximisation de la valeur nette actualisée) a permis de rationaliser les conditions optimales d’immobilisation. Une économie de l’ordre de 50% sur les coûts générés tout au long du temps de vie du procédé a pu ainsi être obtenue. En conditions de transestérification continue, aucune différence dans le profil de produits par rapport à Novozyme 435 n’a été observée. Finalement, une alternative à la transestérification directe de l‘huile a été envisagée. Une première phase d’hydrolyse de l’huile est suivie d’un procédé de récupération des acides gras qui sont dans un second temps estérifiés enzymatiquement. Pour réaliser cette dernière étape, le meilleur système réactionnel s’est avéré être le milieu sans solvant. Un réacteur continu d’estérification de l’acide oléique avec l’isobutanol a été optimisé. Cela a permis un réacteur stable pendant 54 jours consécutifs et respectant les critères des biotechnologies blanches. Une productivité annuelle de 126 tonnes.kg de Novozyme 435-1 a été atteinte. Cela représente une amélioration de la productivité d’un facteur 9,2 par rapport au procédé de transestérification développée précédemment / This work focused on the development of efficient continuous processes for the production of esters from crude or refined high oleic sunflower oil with enzymatic packed bed reactor presenting high levels of productivity and stability. A process of continuous transesterification in packed bed reactor using Novozyme 435 (lipase B from Candida antarctica immobilized onto Lewatit VP OC 1600), a non-specific biocatalyst, was optimized to transformation of high-oleic sunflower oil into butylic esters. The phenomena of partition of polar compounds (phospholipids found in crude oils, produced glycerol etc.) between the reaction medium and the enzymatic support were managed using tert-butanol, a polar solvent. The conditions that enabled the best compromise between stability, productivity and production yields were obtained with an initial oil concentration of 500 mM and a molar ratio between co-substrates of 5. Such conditions enabled a productivity of 13.8 tons.kg-1.kg of Novozyme 435-1 to be reached. The reactor exhibited great stability for 50 consecutive days without any loss of activity. That enabled to minimize the high costs of the enzyme. The novelty of the process was the use of crude oils, containing high levels of natural antioxidants (phospholipids, tocopherols etc.). We demonstrated that these minor components of oils were preserved during the transesterification process. It conferred the synthesized esters some remarkable properties of oxidative resistance.The economic relevance of the process was improved thanks to the development of a new biocatalyst onto a very hydrophobic support (Accurel MP) in order to avoid any adsorptions of polar compounds. An economic analysis (maximisation of the net present value) enabled to rationalize the optimal immobilisation conditions. Over the whole process, it enabled a 50% saving on the global expenses.__ In continuous transesterification conditions, no difference in the product profile was noticed between the new biocatalyst and Novozyme 435.Finally, an alternative to direct transesterification of oil was considered. A first stage of oil hydrolysis is followed by a process of fatty acid recovery and a stage of enzymatic esterification into esters. In order to realize/complete this last stage, the best reaction system was a solvent-free medium. A continuous reactor for the esterification of oleic acid with isobutanol was optimized. It enabled a reactor stable/a stable reactor for 54 consecutive days, respecting the conditions of white biotechnologies. An annual productivity of 126 tons.year-1.kg of Novozyme 435-1 was reached. That represented a productivity improvement by a factor of 9.2 in comparison with the transesterification process.

Les travaux présentés dans ce manuscrit de doctorat s'inscrivent dans la thématique du stockage inter-saisonnier de l'énergie solaire thermique pour l'habitat et le tertiaire (eau chaude sanitaire et chauffage). Le stockage thermochimique en air humide est une des solutions les plus prometteuses, en particulier avec un réacteur à lit fixe. Le bromure de strontium et l'alun de potassium ont été sélectionnés comme réactifs pour leurs caractéristiques énergétiques lors de réactions d'hydratation et de déshydratation. L'étude est constituée d'avancées théoriques, de nombreuses expérimentations et d'un modèle numérique détaillé. Une étude thermodynamique a démontré l'existence d'une droite de charge qui relie les conditions d'entrée et de sortie de l'air humide au passage du réactif. Les équations régissant les réactions chimiques, les transferts massiques et thermiques et la conservation de la quantité de mouvement ont été établies et un modèle numérique monodimensionnel couplant ces phénomènes a été développé. Des essais sur différents échantillons des deux sels et pour divers conditions opératoires ont été effectués dans le but de comprendre les phénomènes physico-chimiques ainsi que pour valider l'étude théorique et le modèle numérique. / This PhD thesis focuses on seasonal solar thermal energy storage for household applications such as production of heat and domestic hot water. Thermochemical storage was chosen for that purpose. The specific solid/gas reactions with water vapor, also called hydration/dehydration reactions, were used with a multi-scale global approach. The level of the reactor was identified as the critical level of that multi-scale approach. As a consequence, the integrated fixed-bed reactor technology in a moist air open loop system was adopted. A theoretical, experimental and numerical methodology was used for the study where strontium bromide and potassium alum salts were chosen as reactive materials. The corresponding reactions are: + 5 (H2O) ↔ (with Δhr=67.4 kJ/molwater and Δsr=175 J/K.molwater) + 9 (H2O) ↔ < KAl(SO4)2.12H2O > (with Δhr=44.2 kJ/molwater and Δsr=109.8 J/K.molwater) The first salt exhibits very good thermochemical properties. On the other hand, the main advantages of potassium alum are its low cost and the fact that it presents no sanitary risk. More than 30 cycles with 3 different samples of potassium alum and more than 25 cycles with 4 samples of strontium bromide under various stationary and dynamic operating conditions were carried out in order to understand the phenomena. The main experimental results were the following ones: • A very good stability and reproducibility of physical and chemical phenomena was observed for both materials. • A thermal reaction front was also observed. • A thermal hysteresis for both salts was found. • Based on that last observation a theoretical equation named charge-discharge line was developed. Experimental results with both salts validate the charge-discharge line theory. • A correlation between reaction kinetics, temperature rise due to the reaction, power of the reaction and the operating conditions was observed. The criterion for that correlation is the affinity of the reaction. A proportional correlation between affinity and reaction kinetics, temperature rise and power of the reaction was observed. • Spontaneous hydration and over-hydration reactions do not produce any particular difficulties or problems. • Pressure drop through the reactor and evolution of salts volume were also measured. Experimental energy density was measured in the range of 350 kWh/m3 for strontium bromide and 240 kWh/m3 for the potassium alum. • In general, strontium bromide is a very good candidate material for seasonal storage, while potassium alum cannot provide satisfying temperature rise and power. The equations governing those phenomena were also established and used to develop a 1D numerical model with partial differential equations coupling chemical phenomena, mass and thermal transfer phenomena and momentum conservation. Verification, validation and confirmation of this model under a very large range of operating conditions were carried out based on the experimental results of strontium bromide. A total of 19 different test cases were studied in order to validate the numerical model. The effect of humidity, temperature, quantity of reactive material and air flow were studied both for stationary and dynamic conditions. The numerical model was able to provide very satisfying results.