Дисертації з теми "Biomass foam"

Harvesting and dewatering can account for up to 30% of the overall cost of production of usable microalgae biomass for the biotechnology and bioenergy sectors. Harvesting is particularly challenging due to the small amount of algal biomass produced relative to water volume. This process exacts high energy and cost demands and therefore limits further expansion in the microalgae biomass industry. Foam fractionation has potential to deliver a low cost, low energy harvesting solution. Microalgae cells adsorb to the surface of a stream of fine air bubbles, which then rise up a closed column, discharging the concentrated product at the top. Foam fractionation significantly reduces construction, maintenance, and energy costs compared to other harvesting technologies. In this research, a fractional factorial design of experiments followed by a central composite design were used to determine the optimal levels of major variables influencing the harvest of the freshwater microalga Chlorella sp. The effects of bubble size within the liquid pool and foam phase of the harvesting unit were determined, a high concentration factor of 427 as achieved using fluidic oscillation for microbubble generation. The influence of microalgal growth phase on harvest efficiency was investigated to gain insight into the optimal time to harvest during cell cultivation. The effect of surfactant, used to induce foaming, on lipid recovery was examined through methods including total lipid recovery, gas chromatography, energy dispersive x-ray spectrometry and solid phase extraction. The results indicate that the surfactant had the additional benefit of significantly increasing the overall lipid recovery. These encouraging results suggest foam fractionation offers considerable potential as an efficient, low cost, and scalable microalgae biomass harvesting technology.

This work reports the pilot-scale investigation of various anaerobic reactor systems treating a fruit washing wastewater. An open cell reticulated foam was used as a biomass support media (BSM). The foam pads (25 mm cubes) were randomly packed in the 2.5 m- 3 reactor with an unpacked section beneath the bed. Four general operational regimes were evaluated. These were: single and two stage operation, with and without effluent recycle. Performance was monitored throughout each run in terms of maximum COD loading rate and minimum attainable hydraulic retention time. Biomass concentrations, both within the media and freely suspended between the biomass support particles were measured on samples from each operating regime, their acetoclastic activity being determined in a laboratory test. A method was developed to ascertain whether a difference in biomass activity existed between the outside of an individual biomass support particle and at the centre of the particle, using a radioactively labelled substrate. It was concluded that a two stage system without recycle provided the best performance with respect to the the maximum attainable loading rate (11.6 kgCOD.m- 3 .day). This was approximately twice that for any of the other systems tested. The minimum hydraulic retention time corresponding to this loading was approximately 1.0 d. The superior performance of the two stage system without recycle was attributed to the increased acetoclastic populations brought about by the pre-acidified feed and the plug flow removal kinetics exhibited in reactors without recycle. Two stage systems produced higher levels of biomass in the reactor than their single stage counterparts and a large proportion of the total biomass inventory was present as suspended growth in systems without recycle. Tracer studies showed that the actual HRT was much less than that calculated from flow rate and reactor volume, indicating that large areas of the reactor were not accessible to the substrate. Experiments investigating activity gradients in the BSM indicated that a significant difference existed between the acetoclastic activity of biomass at the centre of a colonized particle and that on the surface. It may be concluded that substrate diffusional limitations played an important role in determining the performance of this type of biomass support. Electron microscope examination of BSP fragments gave little information other than the existence of both attached and suspended growth. Most of the bio mass was present as a dense fibrillar network.

Este projeto estudou a influência do substrato na dinâmica do processo de formação do biofilme em espuma de poliuretano, em reatores anaeróbios horizontais de leito fixo diferenciais, alimentados com extrato de carne, glicose, amido, lipídeos e esgoto sanitário sintético. O estudo constitui em acompanhar a colonização das matrizes de espuma, ao longo do tempo, em relação a quantidade de biomassa aculumada, polímero extracelular produzido e características morfológicas das células presentes nos suportes retirados dos reatores diferenciais. O uso dessas técnicas permitiu o melhor entendimento do processo de aderência, além da verificação da composição morfológica e a estrutura do biofilme aderido ao suporte, possibilitando correlacionar a ocorrência de determinadas morfologias com cada etapa da colonização observada. A influência do substrato na dinâmica de aderência foi verificada devido aos diferentes padrões de colonização encontrados. Foi observada uma grande variabilidade morfológica em relação ao substrato utilizado. Todavia, uma grande ocorrência de organismos semelhantes a Methanosaeta sp foi verificada em todos os ciclos, principalmente em relação a Methanosarcina sp. O fenômeno de excreção de polímeros pareceu ser de fundamental importância no processo de colonização de matrizes de poliuretano, estando vinculado provavelmente à fixação das células aos suportes. A produção de polímeros, na etapa de aderência inicial, apresentou comportamento diferenciado para cada substrato utilizado. De acordo com os modelos propostos e as análises de microscopia eletrônica de varredura, verificou-se que os polímeros extracelulares podem estar ligados ao entupimento de reatores de leito fixo, permanecendo no interior dos suportes e nos interstícios do leito, causando problemas operacionais. As rápidas partidas observadas em trabalhos utilizando reatores de leito fixo e espuma de poliuretano como suporte podem estar vinculadas à rápida aderência dos organismos em todos os ciclos estudados.
This work focused on the influence of the type of substrate on the process of biofilm formation onto polyurethane foam matrices, in differential horizontal anaerobic immobilized sludge reactors, fed with meat extract (protein), glucose, starch, lipid and synthetic domestic wastewater. It consisted of accompanying the colonization of foam matrices with time, regarding to biomass amount, extracellular polymers produced and the morphological characteristics of the cells present on the supports packed in the differential reactors. These techniques permitted a better understanding of the adhesion process, besides a verification of the morphological composition and the structure of the biofilm attached to the support, making possible a correlation of the particular morphologies occurrences with each colonization step. The influence of the substrate was verified due to the different colonization patterns found. It was observed considerable morphological variety depending on the substrate utilized. However, the presence of Methanosaeta sp.- like organisms was often verified in all cycles, specially Methanosarcina sp. The excretion of polymers seemed to be crucial in the colonization process of the polyurethane matrices, being probably related to the cell fixation on the support. The polymeric production, in the inital adhesion step, showed a particular behavior for each substrate employed. According to the proposed models and the scanning electronic microscopy analysis, it was verified that the extracellular polymers can be related to the clogging of the fixed-bed reactors, as it keeps into the supports and the bed interstices, causing operational problems. The fast start-ups observed in works using fixed-bed reactors and polyurethane foam as support can be related to the fast cell adhesion during all cycles studied.

A atividade industrial diversificada tem sido responsável pelo lançamento, no ambiente, de resíduos que contém materiais tóxicos e/ou de difícil degradação. Benzeno, tolueno, etilbenzeno e xilenos (BTEX) são compostos importantes, por estarem presentes em águas superficiais e subterrâneas, geralmente a partir de contaminações por derivadas de petróleo. Enquanto a degradação aeróbia de BTEX já está amplamente entendida e descrita, a aplicação de processos anaeróbios de tratamento, indicados na década de 80 ainda requer mais estudos. Reatores anaeróbios horizontais de leito fixo de bancada preenchidos com cubos de espuma de poliuretano, contendo lodo anaeróbio proveniente de diversas fontes trataram a água residuária sintética a base de proteínas, carboidratos, lipídios, contendo solução etanólica de BTEX e solução de BTEX em detergente comercial; e solução etanólica de BTEX como únicas fontes de carbono. A influência da adição de nitrato e sulfato como aceptores de elétrons na degradação anaeróbia também é discutida. Os reatores foram capazes de remover BTEX nas concentrações testadas de até 15,0 mg/L de cada composto, com tempos de detenção hidráulica de 11,4 horas e 13,5 horas. Os reatores forneceram condições excelentes para o desenvolvimento de biofilme complexo capaz de degradar BTEX, contendo organismos degradadores de BTEX, acetogênicos, acetoclásticos e hidrogenotróficos. Arqueas metanogênicas representaram menos de 0,5% do total de organismos anaeróbios na biomassa dos reatores. O modelo cinético de primeira ordem com residual foi o que melhor representou os dados experimentais e as velocidades de degradações de BTEX, estimadas neste trabalho, foram cerca de 10 a 94 vezes maiores que as encontradas na literatura, em ensaios realizados em microcosmos.
The diversified industrial activity has been responsible for discharge in the environment of toxic and/or difficult degradation compounds. Benzene, toluene, ethylbenzene and xylenes (BTEX) are important compounds present in surface and ground waters, usually from petroleum products contamination. While BTEX aerobic degradation is extensively understood and described, anaerobic treatment application, started in the eighties, associated to fundamental studies need to be improved. Bench-scale horizontal-flow anaerobic immobilized biomass reactors filled with polyurethane foam matrices, containing immobilized anaerobic biomass from various sources, treated synthetic substrate containing protein, carbohydrates, lipids, BTEX solution in ethanol and BTEX solution in commercial detergent, as well as BTEX solution in ethanol as the sole carbon source. The influence of the addition of nitrate and sulfate as electron acceptors on anaerobic degradation is also discussed. The reactors were able to remove up to 15.0 mg/L of each BTEX compound, with hydraulic detention time of 11.4 hours and 13.5 hours. The reactors provided excellent conditions for developing a complex biofilm with BTEX-degraders, acetogenic, acetoclastic and hydrogenotrophic microorganisms. Methanogenic archaea were found to represent less than 0.5% of the total anaerobic organisms in the biomass inside the reactors. Residual first order kinetic model fitted well the experimental data and the BTEX degradation rates, estimated in this work, were about 10- to 94-fold higher than those found in the literature, in microcosms studies.

Optical methods play an important role in process analytical technologies (PAT). Four examples of optical process and quality sensing (OPQS) are presented, which are based on three important experimental techniques: near-infrared absorption, luminescence quenching, and a novel method, photon density wave (PDW) spectroscopy. These are used to evaluate four process and quality parameters related to beer brewing and polyurethane (PU) foaming processes: the ethanol content and the oxygen (O2) content in beer, the biomass in a bioreactor, and the cellular structures of PU foam produced in a pilot production plant.

Este trabalho apresenta e discute os resultados obtidos na operação de quatro reatores anaeróbios operados em bateladas seqüenciais, projetados em escala piloto, para tratamento de 7,8 m3.dia-1 de esgotos sanitários, coletados da rede coletora que atravessa o Campus da USP de São Carlos. Cada sistema (1,2 m3) foi concebido para tratamento de 1,95 m3.dia-1 de esgoto sanitário, com concepções geométricas (relação L-altura/D-diâmetro), mecânicas (agitação mecânica ou recirculação de líquido) e tipo de retenção de biomassa diferentes. Três unidades eram do tipo ASBR (anaerobic sequencing batch reactor) e outro tipo ASBBR (anaerobic sequencing batch biofilm reactor) com leito fixo composto de matrizes cúbicas de espuma de poliuretano. Os ciclos operacionais tinham duração de oito horas perfazendo no total três ciclos por dia em cada sistema. O monitoramento dos reatores incluiu a determinação de DQO, pH, sólidos em suspensão totais (SST) e voláteis, ácidos voláteis totais, alcalinidade no afluente e efluente, bem como a concentração de metano no biogás. O ensaio experimental foi dividido em duas etapas distintas, sendo que na primeira (227 dias), os reatores não receberam inóculo e na segunda (66 dias) houve a inoculação prévia de lodo anaeróbio granular. Em ambas etapas, os dois reatores ASBR com mesmo tipo de agitação por recirculação de líquido, mas com diferente relação L/D não apresentaram desempenho satisfatório. Os valores médios de eficiência de remoção de DQO e de SST foram próximos de 40% e 60%, respectivamente. No efluente a concentração média foi de 300 mgDQO/L e de 100 mgSST/L. Nos reatores, ASBR com agitação mecânica e, ASBBR com biomassa imobilizada, os resultados médios obtidos foram melhores. O reator ASBBR atingiu eficiência média de 65% e 75% em remoção de DQO e SST, enquanto no ASBR com agitação mecânica chegou-se a 60% e 85%, respectivamente. A concentração média no efluente dos reator foi de 150 mgDQO/L e 60 mgSST/L no ASBBR e 220 mgDQO/L e 50 mgSST/L no ASBR com agitação mecânica.
This study reports and discuss several data obtained using four pilot scale anaerobic sequencing batch reactor, treating 7.8 m3.d-1 of domestic sewage from the Sao Paulo University sewer treatment system (Campus- São Carlos). Each reactor system (1.2 m3) was designed for the treatment of 1.95 m3.d-1 of domestic sewage with different geometric reactor characteristics (ratio L-length/D-diameter), mechanical (mechanical mixing or liquor re-circulation) and biomass retention type. Three reactors were a conventional ASBR (anaerobic sequencing batch reactor) with granular biomass and another one, an anaerobic sequencing batch biofilm reactor (ASBBR), which was composed with cubic matrices of polyurethane foam. The reactors were operated within 8-h of a sequential batch cycle, which were attained in three cycles by day for each system. Chemical oxygen demand (COD), pH, total suspended solids (TSS), volatile fatty acids, bicarbonate alkalinity in both the influent and effluent were monitored in the different cycles. Methane concentration was also assessed in the same period using Gas Chromatography (GC). The experiments were divided in two different phases. In the first phase, which corresponded to 227 d, the reactors were not inoculated. In the second phase (66 d) the reactors were then inoculated with anaerobic granular sludge. It was observed that in both operational phases, the two ASBR reactors, with the same re-circulating process of the mixed liquor, but with different L/D ratio, showed non-satisfactory results. The average values of COD and TSS removal were close to 40 and 60%, respectively. In the effluent, the average values were of 300 mgDQO/L and 100 mgTSS/L. ASBR reactors with mechanical mixing and ASBBR reactor with immobilized biomass showed better results. The average removal efficiency observed was of 65 and 75% for COD and TSS, respectively. ASBR reactors with mechanical mixing reached the efficiency of 60 and 85% for COD and TSS removal. The average concentration in the effluent was of 150 mgDQO/L and 60 mgSST/l in the ASBBR reactor; and 220 mgCOD/L and 50 mgTSS/L in the ASBR reactor with mechanical mixing.

O projeto consistiu na concepção e avaliação do desempenho de um sistema anaeróbio-aeróbio para tratamento de esgoto sanitário. O leito do reator foi dividido em quatro compartimentos de igual volume. Foi usada espuma de poliuretano para imobilização da biomassa e, para facilitar a partida do reator, esse material suporte foi previamente inoculado. O projeto teve três fases distintas: na primeira etapa, foi observada a importância da concentração de biomassa anaeróbia no desempenho de reator anaeróbio a princípio operado com metade do leito reacional com espuma e, a seguir, com o leito todo preenchido com espuma. Na segunda etapa, foram testados diferentes tempos de detenção hidráulica no reator que operou apenas em condições anaeróbias. Na última etapa foi operado o reator combinado anaeróbio-aeróbio. Ficou constatada a importância da concentração de microrganismos no desempenho do reator anaeróbio, pois com o aumento da quantidade de espuma, o reator atingiu resultados melhores e maior estabilidade operacional. Foi comprovada a influência do tempo de detenção hidráulica (TDH) no desempenho do reator. Tempos de detenção muito altos acarretam problemas de transferência de massa líquido-sólido, e baixos TDH dificultam adequada ação dos microrganismos. O melhor resultado para o reator em operação exclusivamente anaeróbia foi para o TDH de 10 horas, no qual se conseguiu reduzir a DQO de amostra bruta de 389 +/- 70 mg/L para 137 +/- 16 mg/L, em média. Para o reator operado anaeróbio-aeróbio a DQO de amostra bruta decresceu de 259 +/- 69 mg/L para 93 +/- 31 mg/L, em média. A comparação de todos os resultados obtidos, evidenciou a importância do pós-tratamento aeróbio na remoção de parcela de matéria orgânica não removida em tratamento unicamente anaeróbio.
The project consisted in the design and performance evaluation of an anaerobic-aerobic system for wastewater treatment. Polyurethane foam was used for biomass immobilization and, to smooth the reactor start-up, this supporting material was previously inoculated. The project was divided in three distinct phases. In the first one, the importance of the anaerobic biomass concentration was observed in the performance of the anaerobic reactor in a way to operate the reactor primarily with half of the reaction bed filled with foam and subsequently operate it with the bed completely filled with foam. In the second phase, different times of hydraulic retention were tested with the reactor operating exclusively in anerobic conditions. In the third and last phase, an anaerobic-aerobic combined reactor was operated. It was possible to confirm the importance of microorganism concentration in the performance of the anaerobic reactor, since the increase in the amount of foam allowed the reactor to reach better results and greater operational stability. The influence of the hydraulic retention time in the reactor performance was also proved. Very high retention times cause problems in the liquid-solid mass transference, while low retention times do not allow an adequate action of microorganisms. The best result for the reactor with an exclusive anaerobic operation was the 10 hour retention time, when it was possible to reduce the COD of a 389 +/- 70 mg/L gross sample to a 137 +/- 16 mg/L in average. On the other hand, for the anaerobic-aerobic operating reactor, the COD of a gross sample dropped from 259 +/- 69 mg/ L to 93 +/- 31 mg/L in average. Finally, comparing all the obtained results, it was possible to verify the importance of the anaerobic post treatment in the removal of a part of the organic matter not removed in an exclusively anaerobic treatment.

O presente trabalho constou da concepção de um reator anaeróbio em regime de batelada com circulação da fase aquosa contendo biomassa imobilizada em espuma de poliuretano. O reator foi operado em ciclos de 8 h e mantido a 30 ± 1ºC tratando água residuária sintética elaborada à base de glicose, com concentração de aproximadamente 500 mgDQO/L. O estudo hidrodinâmico realizado com velocidade superficial de recirculação entre 0,16 e 0,80 cm/s indicou que o tempo de mistura obtido em todas as condições pode ser considerado desprezível quando comparado ao tempo total do ciclo, e também permitiu considerar o comportamento do escoamento no leito como o de um reator pistonado. O desempenho do reator no tratamento da água residuária foi avaliado para a condição sem circulação e também para velocidades superficiais de recirculação entre 0,03 e 0,30 cm/s. Os resultados obtidos indicaram que o reator apresentou desempenho satisfatório e boa estabilidade, apresentando eficiências de até 96% de remoção da matéria orgânica. O aumento da velocidade superficial de recirculação diminuiu a resistência a transferência de massa na fase líquida, ocasionando um aumento de 115% na velocidade global de reação, estimada através do ajuste dos valores experimentais da concentração de substrato ao modelo de primeira ordem.
A new configuration of an anaerobic bioreactor with external circulation of the liquid phase wherein the biomass was immobilized on a polyurethane foam matrix is proposed. 8-hours cycles were cartied out at a temperature of 30 ± 1°C treating glucose synthetic wastewater at a concentration around 500 mg/L. A hydrodynamic study performed at 0.16 to 0.80 cm/s showed that the obtained mixture time is insignificant compared to the total cycles time, and the flow through the polyurethane foam bed can be represented by a plug flow. The reactor\'s performance assessed without circulation and with circulating liquid superficial velocity between 0.03 and 0.30 cm/s. The reactor attained operating stability and a COD removal efficiency of 96% was achieved. The increase in the liquid superficial velocity decreases the liquid resistance mass transfer, resulting in an increase of 115% in the global reaction velocity, estimated through the fit of a first model equation on the substrate concentration experimental values.

Avaliou-se a influência da recirculação da fase líquida e do regime de alimentação em reator anaeróbio no tratamento de esgoto sanitário. Utilizou-se um reator anaeróbio operado em bateladas seqüenciais, contendo biomassa imobilizada (ASBBR), em escala piloto, com volume total de 1,2 \'M POT.3\' (\'fi\' 1,0 m e altura 1,53 m). O leito suporte para a imobilização da biomassa era constituído por matrizes cúbicas de espuma de poliuretano, com 5 cm de aresta, confinadas em cesto de aço inox 304, colocado no interior do reator. A influência da recirculação da fase líquida sobre o desempenho do ASBBR quanto à remoção de matéria orgânica e quanto ao arraste de sólidos foi avaliada submetendo-se o reator às velocidades ascensionais de 1,27; 3,82; 7,64 e 10,18 m/h resultantes das diferentes vazões de recirculação impostas. Contrariamente ao observado em pesquisas anteriores em reatores operados em escala de bancada e alimentados com água residuária sintética, não houve aumento significativo da eficiência do reator com o aumento da velocidade ascensional no tratamento de esgoto sanitário. A influência do regime de alimentação de esgoto sanitário no desempenho do ASBBR foi avaliada submetendo-se o reator a tempos de enchimento correspondentes a 0,25 e 0,5 do tempo total de ciclo, utilizando-se a vazão de recirculação de 6 \'M POT.3\'/h, que foi a que apresentou os melhores resultados nos ensaios anteriores. Concluiu-se que o reator pode ser operado sob batelada alimentada com duração de até 0,5 tempo de ciclo, sem que seu desempenho seja significativamente alterado. Esse resultado é importante, pois representa que o sistema de tratamento composto por reatores ASBBR pode ser projetado com número menor de reatores. A fim de esclarecer dúvidas sobre o desempenho do ASBBR observado no tratamento de água residuária de composição complexa (esgoto sanitário), o reator foi alimentado com água residuária facilmente degradável (etanol). O desempenho do reator foi aquém do esperado, mesmo quando alimentado com composto de fácil degradação. Os ensaios de atividade metanogênica específica (AME) demonstraram que houve decréscimo dos valores de AME com o aumento da velocidade ascensional. Os valores obtidos foram 0,0632; 0,0509; 0,0248 e 0,0299 g DQO-CH4/(g STV.d), respectivamente, para os valores de Va de 1,27; 3,82; 7,64 e 10,19 m/h. Concluiu-se que a baixa eficiência de remoção de matéria orgânica deveu-se ao abaixamento progressivo da atividade metanogênica do lodo, cujas causas não puderam ser completamente esclarecidas nesta pesquisa.
The influence of the liquid phase recirculation and the feeding regimen on the performance of an anaerobic sequencing batch reactor containing immobilized biomass (ASBBR) applied for the treatment of domestic sewage was evaluated. Biomass immobilization was provided by a basket containing cubic polyurethane foam matrices (5 cm side) inside the 1.2 \'M POT.3\' (1.0 m diameter and 1.53 m height) pilot-scale reactor. The influence of the liquid phase recirculation on the reactor performance in respect to organic matter and solids wash-out was verified by subjecting the reactor to a wide range of up flow velocities (1.27; 3.82; 7.64 and 10.18 m/h) resulting from different recirculation flow rates imposed. The increase of the up flow velocity did not increase the efficiency of the pilot reactor as expected. This result contradicts those obtained with bench-scale ASBBR experiments treating synthetic wastewaters. The influence of the feeding regimen was verified by subjecting the reactor to feeding times correspondent to 0.25 and 0.50 of the total cycle time, at the recirculation flow rate of 6 \'M POT.3\'/h. It could be concluded that the reactor can be operated at the feeding batch mode up to 0.5 of the cycle time. This result is important for full scale applications considering that a treatment system composed of ASBBR reactors can be designed using a lower number of units. In order to clear some aspects related to the limited performance of the ASBBR reactor treating a complex wastewater (sewage), the reactor was subjected to an easily degradable wastewater (ethanol). However, the performance was not improved even when the reactor was treating an easily degradable compound. The results from the specific methanogenic activity (SMA) demonstrated a decrease on the values of SMA with the increase of the up flow velocity. The values of SMA were 0.0632; 0.0509; 0.0248 and 0.0299 g DQO-CH4/(g STV.d) for the Va of 1.27; 3.82; 7.64 and 10.19 m/h respectively. It could be concluded that the low efficiency obtained for organic matter removal was due mainly to the progressive decrease of the sludge methanogenic activity. The causes for that behaviour could not be completely explained in this research. It could be concluded that the reactor performance was iv clearly limited by the low productivity of the methanogenic populations present in the biomass.

Ce travail décrit la synthèse d'une série de matériaux à base de biomasse d'alginate et d'algues; ces matériaux ont été conçus sous différentes formes: billes et mousses. Des procédés spécifiques ont été mis au point pour l’utilisation directe de la biomasse algale (AB, sans ajout d’autres polymères) avec le souci de développer un processus de synthèse simple et respectueux de l’environnement (production réduite de sous-produits et sans additif supplémentaire). Ces matériaux ont été testés pour la décontamination d’effluents contenant des métaux lourds (Pb(II) et Cu(II)), mais également pour la valorisation des métaux (métaux du groupe platine, PGM: Pd(II) et Pt(IV)). Différents paramètres opératoires ont été testés afin d'évaluer les capacités de sorption et les étapes limitantes, mais également d'identifier des stratégies d’amélioration des performances d’adsorption. L’incorporation de poly(éthylèneimine) (PEI) est une méthode prometteuse pour augmenter la densité de groupes réactifs (fonctions amines). Différents procédés ont été testés: (a) l'incorporation de particules de PEI réticulées avec du glutaraldéhyde (billes hétérogènes: ABA/PEI), et (b) le greffage homogène de PEI sur de l'alginate (suivi de la réticulation par le glutaraldéhyde) (billes homogènes HABA/PEI). La spectroscopie FTIR et l'analyse MEB& MEB-EDX ont été utilisées pour interpréter les mécanismes de fixation ainsi que pour caractériser la structure des matériaux. Dans une deuxième étape, les matériaux sélectionnés ont été testés pour la catalyse supportée en utilisant la réaction d'hydrogénation du 3–nitrophénol (3-NP). Les résultats sont structurés en 3 parties développées successivement: (a) synthèse des billes d’alginate, AB et AB/PEI et étude de l’adsorption de métaux lourds et de PGMs, (b) comparaison des propriétés d’adsorption du Pd(II) par les billes composites AB/PEI préparées par les voies homogène et hétérogène (et leur application aux tests en catalyse supportée), et (c) la synthèse de mousses poreuses (préparées par réaction entre l’alginate et la PEI) appliquées à l’adsorption du Pd(II) et à la catalyse supportée en réacteur à lit fixe.Si la PEI a un effet limité sur la fixation des métaux lourds (interaction avec les groupes carboxyliques de la biomasse d'alginate ou d'algues), sa présence améliore l’adsorption des métaux dans le cas des PGMs (les groupes amine protonés ont une forte affinité pour les espèces chloro-anioniques du Pd(II)) en particulier pour les billes d'alginate et AB. Tous les adsorbants ont une préférence pour le Pb(II) par rapport au Cu(II) et pour le Pd(II) par rapport au Pt(IV); la présence de PEI limite la sélectivité du matériau pour le Pb(II) et le Pd(II). La capacité de fixation et la stabilité des billes composites d'alginate/PEI ont été améliorées en utilisant le mode de synthèse homogène (la PEI étant dispersée de manière homogène dans la bille avant la réticulation par le glutaraldéhyde). Les deux supports (billes hétérogènes ou homogènes) chargés en Pd(II) (ensuite réduit) ont permis des performances catalytiques comparables bien qu’inférieures à celles des catalyseurs classiques, mais le mode homogène améliore la stabilité à long terme du matériau. Le conditionnement du support catalytique sous forme de mousse a permis de tester la réaction catalytique dans un système à lit fixe : le conditionnement sous forme de mousse améliore les propriétés de transfert de masse par rapport aux billes et la constante de vitesse apparente n'est que légèrement réduite après 30 cycles de fonctionnement
This work describes the synthesis of a series of materials based on alginate and algal biomass (AB); these materials have been designed under different shapes: beads and foams. Special processes have been developed for directly using the algal biomass (without adding other polymers) with the double objective of simple processing and environmentally-friendly manufacturing (reduced production of sub-products and without additional resources). These materials have been tested first for metal recovery for heavy metal decontamination (Pb(II) and Cu(II)) but also for the valorization of metals (platinum groups metals, PGMs: Pd(II) and Pt(IV)). These studies were performed investigating various operating conditions in order to evaluate sorption capacities and limiting steps but also to identify the processes to be used for improving sorption performance. The incorporation of poly(ethyleneimine), PEI, is a promising method for increasing the density of highly reactive groups (amine functions). Different processes have been tested: (a) the incorporation of particles of PEI crosslinked with glutaraldehyde (heterogeneous beads: ABA/PEI), and (b) the homogeneous grafting of PEI on alginate (followed by glutaraldehyde crosslinking) (HABA/PEI beads). Several techniques have been used for characterizing the sorption process and the structure of developed sorbents, including FTIR spectroscopy, SEM & SEM-EDX analysis. In a second step selected materials have been tested for supported catalysis using the simple reaction of hydrogenation of 3–nitrophenol (3-NP) as a test reaction. The results are structured in 3 parts successively developed: (a) synthesis of alginate, AB and AB/PEI beads and testing for sorption heavy metals and PGMs, (b) comparison of Pd(II) sorption properties of AB/PEI composite beads prepared by the homogeneous and the heterogeneous routes (and their application to supported catalytic tests), and (c) synthesis of highly porous foams (prepared by reaction of alginate with PEI) and the testing of Pd(II) sorption and Pd-supported catalysis (in fixed-bed reactor). While PEI hardly affects the sorption of heavy metals (due to direct interaction with carboxylic groups of alginate or algal biomass), the presence of PEI strongly improves metal binding in the case of PGMs (the protonated amine groups strongly bind chloro-anionic PGM species). All the sorbents have a preference for Pb(II) over Cu(II) and for Pd(II) over Pt(IV), especially for alginate and AB beads because the presence of PEI limits the selectivity of the material for Pb(II) and Pd(II). Both the sorption capacity and the stability of composite alginate/PEI beads were improved while using the homogeneous synthesis mode (the PEI polymer being homogeneously dispersed in the bead before glutaraldehyde crosslinking). The two supports (heterogeneous vs. homogeneous beads) loaded with Pd(II) and subsequently reduced gave comparable catalytic performance (lower than conventional catalysts) but the homogeneous mode improves the long-term stability. The conditioning of the catalytic support as a foam allows testing the catalytic reaction in fixed-bed system: the conditioning improves mass transfer properties compared to beads and the apparent rate constant is only slightly reduced after operating 30 cycles

Métodos de Microbiologia de anaeróbios estritos e de Biologia Molecular foram empregados para se conhecer a diversidade de microrganismos relacionados à degradação de ascarel em reatores anaeróbios metanogênicos. A avaliação de potencial metanogênico foi realizada para a escolha da melhor condição nutricional, bem como, para a seleção de material suporte e solvente adequado a solubilização do ascarel. Nos ensaios em batelada, a produção de metano foi maior nos reatores contendo etanol (média de 0,22 - 0,46 molCH4/gSTV, 46h). Remoção de 85,6% (86,7 mg/L de PCB em Aroclor 1016 e 1260) foi obtida na condição com espuma de poliuretano, etanol (46g/L) e formiato (680 mg/L). Diferentes solventes e surfactantes, tais como, DMSO, dioxano, ácido acético, ácido fórmico, n-hexano, acetona, etano, metanol, Tween 80, SDS (10%) e Triton X-100 foram avaliados para a solubilização de ascarel. Dentre esses, metanol, Triton X-100 e ácido fórmico foram eleitos para a realização de ensaio em reatores em batelada contendo espuma de poliuretano, com o propósito de avaliar o potencial metanogênico na degradação de PCB. Os valores de produção de metano foram muito semelhantes (0,21 0,38 molCH4/mLgSTV, 45h) nas diferentes condições, no entanto, a remoção de PCB foi maior nos reatores com metanol 790 mg/L (86,6%), ácido Fórmico 600 mg/L (84,5%) e Triton X-100 1% (72,1%). Portanto, a melhor condição foi contemplada para a operação do reator anaeróbio horizontal de leito fixo (RAHLF) no tratamento do ascarel, ou seja, células imobilizadas em espuma de poliuretano, etanol e formiato (como fonte de carbono), Triton X-100 (0,1%) e metanol (como solvente). No RAHLF, a remoção média de matéria orgânica (DQO) foi de 91% para concentração afluente média de 1270 mg/L. A presença de morfologias semelhantes à Methanosarcina e bacilos fluorescentes foi confirmada em exames microscópicos. Na análise filogenética, por meio de PCR/DGGE e seqüenciamento das bandas recortadas, os grupos encontrados foram relacionados aos Filos Proteobacteria, Firmicutes, Spirochaetes, Chlorobi e Chloroflexi, sendo que neste último estão incluídos representantes relacionados a degradação de PCBs. Dentre as arquéias metanogênicas verificou-se similaridade de 99% e 97% com Methanosaeta sp. e Methanolinea sp., relacionadas com a metanogenese acetoclástica e hidrogenotrófica, respectivamente
Molecular biology and microbiology methods were used to study the microbial communities related to degradation of ascarel at methanogenic conditions in an anaerobic reactor. The methanogenic potential was evaluated to choose the better nutritional condition as well as to select the better support material and the most suitable solvent to favor the solubilization of ascarel. The methane production was higher (0.22 0.46 molCH4/mLgSTV, 46h) in batch reactors containing ethanol (46 g/L) and formate (680 mg/L), the PCB elimination attaining 85.6% (86.7 mg/L de PCB as Aroclor 1016 and 1260) when Polyuretane foam was used as support material. Different solvents, namely DMSO, dioxane, n-hexane, acetic acid, formic acid, acetone, ethane, methanol, and surfactants, such as 10% SDS,, Triton X-100, were evaluated aiming o determine the better condition to solubilize ascarel. According to the results of such experiments, methanol, formic acid and Triton X-100 were selected for carrying out the batch experiments in reactors containing polyurethane foam to evaluate the methane production during the PCBs degradation. Regardless of the operation conditions the methane production rates were similar (0.21 0.38 molCH4/gSTV, 45h), however the elimination of PCB was higher in the reactors containing methanol (790 mg/L), formic acid (600 mg/L) and Triton X-100 (1%). Therefore, the better condition for treating ascarel-containing residues in a bench-scale horizontal-flow immobilized biomass (HAIB) was attained with cells immobilized in polyurethane foam when ethanol and formate were used as carbon sources, and in presence of Triton X-100 and methanol, the average elimination of organic material attaining 91% for affluent concentration of 1270 mg/L. The presence of Methanosarcina and fluorescent rods was confirmed by microscopy analysis. According to the filogenetics analysis, which was carried out by PCR/DGGE and band-sequencing, the Bacteria domain are related to the Filos Proteobacteria, Firmicutes, Spirochaetes, Chlorobi and Chloroflexi, this latter being directly related to the degradation of PCB. Among the methanogenic Archea, a similiraty of 99% and 97% was observed to Methanosaeta sp. and Methanolinea sp. related to acetoclastic and hydrogenthrophic methanogenesis, respectively

Cette recherche s'est concentrée sur les bioressources, notamment le tanin, la lignine, les protéines de soja, les humines, pour préparer des adhésifs et des mousses à base de bois bio. Il y a quatre parties principales, dont deux types de préparation de colles à bois en utilisant des bio-ressources, à savoir les colles à bois NIPU biosourcées et les colles à bois biosourcées (tanin, SPI et lignine) sans formaldéhyde toxique ; deux types de produits de mousse de tanin, c'est-à-dire une mousse de tanin-furanique typique et des mousses de polyuréthane sans isocyanate. (1) Les humines commerciales, l'isolement de protéines de soja (SPI) et le tanin de mimosa ont été utilisés pour préparer des adhésifs pour bois, basés sur la formulation de polyuréthanes non-isocyanates (NIPU). Les propriétés de base des adhésifs ont été déterminées. Des techniques telles que MALDI-ToF et FTIR ont été utilisées pour détecter les produits obtenus et pour analyser les mécanismes réactionnels impliqués. Une analyse thermomécanique (TMA) a été utilisée pour étudier le comportement thermique des adhésifs. Enfin, des contreplaqués ou des panneaux de particules de laboratoire ont été préparés pour évaluer les performances de collage des adhésifs. (2) Un nouvel adhésif pour bois à base de biomasse a été préparé avec un extrait de tanin de mimosa commercial et de l'éther diglycidylique de glycérol (GDE) par mélange mécanique pratique. Le GDE a servi d'agent de réticulation du tanin sans aucune addition d'aldéhyde, produisant des réseaux tridimensionnels durcis. Différents rapports pondéraux tanin/GDE ont été étudiés par plusieurs techniques pour déterminer leur influence sur les propriétés finales. Deux types d'adhésifs à base de lignine ont été préparés, c'est-à-dire (ⅰ) la lignine modifiée au glyoxal et l'amidon dialdéhyde réticulé par l'urée; (ⅱ) oxydation du periodate en deux étapes. Les espèces moléculaires formées et le mécanisme réactionnel impliqué ont été déterminés par FT-IR, RMN 13C et spectrométrie de masse MALDI-ToF. Les adhésifs basés sur cette réaction ont été testés par collage de contreplaqué ou de panneaux de particules de laboratoire, par calorimétrie différentielle à balayage (DSC) et analyse thermomécanique (TMA).(3) Une mousse rigide de polyuréthane sans isocyanate (NIPU) à base de tanin a été obtenue. Le mélange d'acide citrique et de glutaraldéhyde a servi d'agent d'expansion et de réticulation utilisé pour fournir de l'énergie moussante et réticuler la résine à base de tanin pour préparer les mousses NIPU. Le mécanisme de réaction des mousses NIPU à base de tanin a été étudié par FT-IR, MALDI-TOF et 13C RMN. De plus, le tanin a également été utilisé comme ignifuge naturel pour améliorer les propriétés finales des mousses NIPU à base de glucose, y compris la résistance au feu et la résistance à la compression. (4) Un déchet de bioraffinerie, des humines et un insolat de protéine de soja (SPI) ont été sélectionnés comme agents de réticulation biosourcés de substitution du formaldéhyde pour deux types de formulations de mousse à base de tanin. Comme attendu, les propriétés ont été améliorées en utilisant ces réticulants biosourcés. Les propriétés de base des mousses de tanin en série ont été étudiées. Les caractéristiques de morphologie et de structure ont été observées par microscopie électronique à balayage (MEB). De plus, les mécanismes de réaction de réticulation entre le tanin avec les deux réticulants bio-sourcés, à savoir les humines et le SPI, ont été déterminés par spectrométrie MALDE-ToF et FTIR. Enfin, la stabilité thermique, les propriétés mécaniques, le caractère ignifuge et l'émission de formaldéhyde ont été évalués par les techniques appropriées
This research was focus on bioresources, including tannin, lignin, soybean protein, humins, to prepare bio-based wood adhesives and foams. There are four main parts, including two kinds of wood adhesives preparation by using bio-resources, i.e., bio-sourced NIPU wood adhesives and bio-based (tannin, SPI, and lignin) wood adhesives without toxic formaldehyde; two kinds of tannin-foam products, i.e., typical tannin-furanic foam and non-isocyanate polyurethane foams. (1) Commercial humins, soybean protein isolation (SPI), and mimosa tannin have been utilized to prepare wood adhesives, based on the formulation of non-isocyanate polyurethanes (NIPU). The basic properties of the adhesives were determined. Techniques such as MALDI-ToF and FTIR were used to detect the products obtained and for analyzing the reaction mechanisms involved. Thermomechanical analysis (TMA) was utilized to investigate the thermal behavior of the adhesives. Finally, the laboratory plywood or particleboard were prepared for evaluating the bonding performances of adhesives. (2) A novel biomass-based wood adhesive was prepared with commercial mimosa tannin extract and glycerol diglycidyl ether (GOE) by convenient mechanical mixing. GOE served as the crosslinker of the tannin without any aldehyde addition yielding hardened three­dimensional networks. Oifferent weight ratios of tannin/GOE were investigated by several techniques to determine their influence on final properties. Two kinds of lignin-based adhesives were prepared, i.e., ( i ) glyoxal modified lignin and dialdehyde starch cross-linked by urea; ( ii ) periodate oxidation by two-steps. The molecular species formed and the reactions mechanism involved were determined by FT-IR, 13C NMR and MALDI-ToF mass spectrometry. The adhesives based on this reaction were tested by bonding laboratory plywood or particleboard, by differential scanning calorimetry (DSC), and thermomechanical analysis (TMA). (3) A tannin-based non-isocyanate polyurethane (NIPU) rigid foam was obtained. Citric acid and glutaraldehyde mixture served as a blowing and crosslinker agent used to provide foaming energy and cross-link the tannin-based resin to prepare the NIPU foams. The reaction mechanism of the tannin-based NIPU foams were investigated by FT-IR, MALDI-TOF, and 13C NMR. Additionally, tannin was also used as a natural tire-retardant to improve the final properties of glucose-­based NIPU foams, including fire retardancy and compression strength. (4) A biorefinery waste, humins, and soybean protein insolate (SPI) were selected as formaldehyde substitute bio-sourced crosslinkers for two kinds of tannin-based foam formulations. As expected, the properties were improved by using these bio-sourced crosslinkers. The basic properties of series tannin foams were investigated. The morphology and structure characteristics were observed by scanning electron microscopy (SEM). Additionally, the crosslinking reaction mechanisms between tannin with the two bio-sourced crosslinkers, i.e., humins and SPI, were determined by MALDE-ToF and FTIR spectrometry. Finally, the thermal stability, mechanical properties, fire retardancy and formaldehyde emission were evaluated by the relevant techniques

Environmental concerns have brought about a push to replace non-biodegradable products that are made from non-renewable resources. Investigations regarding use of wood fibers and other biomass as a raw material for biodegradable foams and sponges are an example of such a replacement. Foams made at least partially of biomass can be created using cellulose from wood fibers once the cellulose is converted into a fluid form. Polyurethane foams can be made from polyols containing as much as 50% biomass by combined dissolution of wood and starch. Sponges can be made completely from cellulose regenerated from a viscose rayon solution, and the effect of using wood fibers as reinforcement material within the cellulose matrix of such sponges was studied. The effect of fiber content and fiber length on absorbance, swelling, density, air to cellulose ratios, bound water, and tensile was determined.

Nesse estudo, procurou-se investigar a influência do aumento de carga orgânica em um ASBR operado a 30ºC, agitado mecanicamente e contendo microrganismos imobilizados em suporte inerte. Para tal, foi aplicado um carregamento orgânico volumétrico variando de 1,5 a 6,0 g DQO/L.dia, alimentando-se um reator construído em acrílico (5,4 L) com 2 L de água residuária sintética com concentrações de 500 a 2000 mg DQO/L com fontes de carboidrato/proteína/lipídio, em bateladas de 8 a 12 h. O sistema apresentou eficiências de remoção de material orgânico entre 73% e 88% para as condições estudadas. Entretanto, quando o reator foi alimentado com uma concentração de 2000 mg DQO/L em bateladas de 8 h, verificou-se o acúmulo de ácidos voláteis totais, refletindo na redução da eficiência de remoção de material orgânico para 55%, para amostras filtradas. Os perfis dinâmicos ao longo da batelada permitiram concluir que, para a condição com o mesmo carregamento orgânico, porém com concentrações afluentes e tempos de ciclo diferentes, a produção inicial de ácidos voláteis totais foi mais acentuada para o caso de alimentação com maior concentração. Para condições com concentrações afluentes iguais, o tempo a mais para o ciclo foi fundamental para obter-se efluente de melhor qualidade em termos de remoção de matéria orgânica.
The current study investigated the effect of increasing organic load in an ASBR operated at 30ºC with mechanical stirring and containing immobilized on inert support. Accordingly, volumetric organic loading rates ranging from 1.5 to 6.0 g COD/L.day were used by feeding an acrylic reactor (5.4 L) with 2 L of influent at concentrations of 500 to 2000 mg COD/L from wastewater containing carbohydrates, proteins and lipids in 8 and 12 h batches. Organic matter removal efficiencies between 73% and 88% were observed under the conditions investigated. However, when the reactor was fed at a concentration of 2000 mg COD/L in 8 h batches, accumulation of total volatile acids was detected, leading to a reduction in organic matter removal efficiency as low as 55% for filtered samples. The dynamic batches profiles allowed to conclude that for the same organic loading rates and different concentration influent and cycle times, the initial production of total volatile acids showed to be more pronounced for better quality effluent in terms of organic matter removal.

In British Columbia, humus form identification is widely use to infer the level of plant-available soil nutrients. This identification is based on field-observable (morphological) features. We recognize three major humu forms: Mors, Moders, and Mulls - which are differentiated according to the type of F horizon, and the presence/absence of organic matter-enriched Ah horizons. Mors represent humus forms where decomposition is dominated by fungi, with slow decomposition rates and accumulations of organic matter on the soil surface. Mors are characterized by the presence of a Fm (m - mycogenous) horizon. In contrast, Mulls represent humus forms with high rates of decomposition and faunal activity resulting in organic matter being intimately incorporated into the upper mineral soil layer instead of accumulating on its surface. Intermediate on the humus form gradient from Mors to Mull are the Moders. Moders are similar to Mors in that they have accumulations of organic matter on the surface of the mineral soil but decomposition is not fungus dominated, so they lack the diagnostic Fm horizon. The central concept of the Moder is represented by the Leptomoder, which is characterized by a Fz (z - zoogenous) horizon with an active population of soil meso- and microfauna, fungal mycelia are not present or present in small amounts. When both fungal mycelia and faunal droppings can be found, but neither clearly predominate over the other, an Fa (a - amphimorphic) horizon results. Fa horizons are characteristic of Mormoders, an integrade between Mors and Moders. Considering the prevalence of Mormoders and Leptomoders in B.C. and the difficulties in identifying Fa horizons, the aim of this study was to determine whether the morphological features used to differentiate these two Moder humus forms reflects differences in their physical, chemical and biotic properties.

Les racines des plantes jouent un rôle important dans la croissance et le développement des plantes, et il est bien connu que les interactions mécaniques entre une croissance racinaire et le sol environnant peuvent avoir un impact majeur sur la croissance des racines et par conséquent sur la production de biomasse végétale. Ces interactions mécaniques sont l'un des nombreux facteurs qui peuvent expliquent la variabilité de l'architecture des racines, y compris les facteurs génétiques, environnementaux et l'instabilité du développement. Mais ce facteur a souvent été sous-estimé. Nous supposons que la structure hétérogène du sol à l'échelle des grains, démontrée par la large répartition des forces, peut influencer d'une manière significative sur les trajectoires de croissance des racines. Ce travail de thèse vise à déterminer comment les grains dans les sols granulaires se réorganisent sous l'action de la croissance des racines, et en retour, comment les forces résultantes agissant sur les apex des racines modifient leur développement, y compris la cinématique de leurs trajectoires. Nous avons développé un modèle numérique 2D de la croissance des racines dans un milieu granulaire en utilisant la méthode des éléments discrets (DEM). Le modèle est capable de calculer les forces de contacts grain-grain et racine-grain dans un milieu granulaire. Le système racinaire est modélisé en utilisant des chaînes d'éléments de spheroline connectés. L'orientation de la croissance des racines, à chaque étape de croissance est déterminée par la dynamique de la racine entière sous l'action des forces élastiques internes et des forces de réaction exercées par les grains, ces sont les interactions mécaniques qui contrôlent la croissance numérique dans le modèle.Des études paramétriques ont été réalisées afin (i) d'estimer l'influence de la structure granulaire (distribution de grains de diamètre, la cohésion, la fraction volumique ...) et les propriétés mécaniques des racines (la rigidité à la flexion) sur le signal de force axiale agissant sur la pointe de la racine, et sur les trajectoires et (ii) de définir les lois physiques générales qui peuvent être utilisées en outre pour analyser des données expérimentales. Les courbes de distribution des forces axiales calculées normalisées par leurs moyens au cours d'une période donnée de la croissance, sont caractérisées par une loi de puissance décroissante pour les forces en dessous de la force moyenne, et une décroissance exponentielle pour les forces ci-dessus de la force moyenne, reflétant ainsi la large répartition des forces à l'intérieur d'un matériau granulaire. Une analyse de l'écart-type des déformations locales des trajectoires des racines, résulte deux régimes en fonction la rigidité de la racine. Une première lorsque le sol contrôle les déformations des racines, et une deuxième lorsque la racine est trop rigide, et se déplace plus les grains environnants durant la croissance
Plant roots play an important role in the growth and development of plants, and it is well known that the mechanical interactions between a growing root and the surrounding soil can have a major impact on root growth and consequently on plant biomass production. These mechanical interactions are one of numerous factors that explain the variability of root architecture, including genetics, environment and developmental instability. But this factor has often been under-estimated. I hypothesize that the heterogeneous structure of soil at the particle scale, demonstrated by the broad distribution of forces, can significantly influence root growth trajectories. This thesis aims at determining how grains in granular soils are reorganized under the action of growing roots, and in return how the resulting forces acting on root tips modify their development, including the kinematics of their trajectories, in order to develop a general biophysical law of root-soil mechanical interactions. I developed a 2D numerical model of root growth in a granular medium using a Discrete Element Model (DEM). The model is able to compute grain-grain and root-grain contact forces within a granular medium. The root system is modelled using chains of connected spheroline elements. The orientation of root growth at every growth step is determined by the dynamics of the whole root under the action of its internal elastic forces and reaction forces exerted by the grains, which are the mechanical interactions that control numerical growth in the model.Parametric studies were carried out in order to (i) estimate the influence of granular structure (grain diameter distribution, cohesion, volume fraction) and root mechanical properties (root bending stiffness) on the axial force signal acting on the root tip, and on the root trajectories and (ii) define general physical laws that can be used further to analyze experimental data. The distribution curves of computed root tip-grain forces normalized by the mean force during a given period of growth were characterized by a decreasing power law for forces below the mean force, and an exponential fall-off for forces above the mean force, thus reflecting the broad distribution of forces inside the granular material. An analysis of the standard deviation of the local deformations of root trajectories resulted in two different regimes with regard root stiffness. In the first regime, soil controlled the root deformation and in the second, the root trajectory was straighter and displaced more significantly the surrounding grains during growth

Os objetivos deste trabalho foram avaliar o desempenho do reator anaeróbio operado em batelada seqüencial quando submetido ao aumento progressivo da concentração de glicose e estimar os parâmetros cinéticos da degradação da glicose. Inicialmente o reator foi operado com ciclos de 8 horas, tratando glicose nas concentrações, aproximadas, de 500, 1000 e 2000 mg/L. Não foi detectada glicose no efluente nas três condições. O reator operou de maneira estável, tratando aproximadamente 500 mg/L de glicose, com eficiência na remoção da DQO filtrada entre 93% e 97%. Na operação com concentrações de glicose no afluente próximas de 1000 mg/L e 2000 mg/L, observou-se instabilidade operacional, principalmente devido à produção de polímeros extracelulares (EPS) que comprometeram a hidrodinâmica e a transferência de massa no sistema. Os valores médios da concentrações de ácidos voláteis no efluente foram de 159 ± 72 mg/L e 374 ± 92 mg/L, respectivamente. Aos perfis de concentração de glicose foi ajustado modelo de primeira ordem, enquanto que um modelo modificado, contemplando concentração residual de matéria orgânica, foi ajustado aos perfis temporais de DQO. Para verificar a formação do EPS, operou-se o reator com 3 horas de ciclo nas concentrações, aproximadas, de 500 e 1000 mg/L. Esta fase teve como objetivo verificar a hipótese, segundo a qual, a produção de EPS seria resultado da exposição da biomassa a baixas concentrações de matéria orgânica por longo período. Dessa forma, reduzindo o tempo de ciclo, a exposição a baixas concentrações também seria reduzida. No entanto, embora o reator tenha operado com relativa estabilidade, verificou-se formação de grande quantidade de EPS logo na primeira condição operacional, com aproximadamente, 500 mg/L de glicose no afluente, indicando que a hipótese não estava correta.
The main objectives of this study were to evaluate the performance of the anaerobic sequencing batch reactor when subjected to a progressive increasing of the influent glucose concentration and estimate the kinetic parameters of glucoses degradation. Initially the reactor was operated with 8-hour cycles, treating glucose at concentrations of 500, 1000 and 2000 mg/L. Glucose was not detected in the effluent in all these three conditions. The reactor showed operating stability treating glucose concentration of approximately 500mg/L, with efficiencies between 93% to 97% in the filtrated COD removal. In the operation with glucose concentrations of 1000 mg/L and 2000 mg/L, approximately, it could be noticed an operational instability, caused mainly by a production of extracellular polymers (EPS) leading to hydrodynamic and mass transfer problems in the reactor. The mean values of volatile acids concentration in the effluent were about 159 ± 72mg/L and 374 ± 92mg/L, respectively. A first order model was adjusted to glucose concentration profiles, and a modified model, including a residual concentration of substrate, was adjusted to COD temporal profiles. To verify the EPS formation, the reactor was operated with 3-hour cycle in the concentrations of 500 and 1000 mg/L This stage had the objective of verifying if the EPS production would result from the exposure of the biomass to low concentration of substrate for a long period of time. Thus, reducing the time cycle, the exposure to low concentrations would also be reduced. Nevertheless, even with the reactor operating with relative stability, the hypotheses could not be verified due the formation of a large amounts of EPS right in the first operational condition with approximately to 500 mg/L of glucose in the influent, showing that the hypothesis was not right.

Le projet Européen UNIfHY a vu le jour dans une optique de production d’hydrogène à partir de biomasse pour le remplacement des énergies fossiles. La purification des gaz produits par la gazéification de la biomasse permet l’obtention d’hydrogène pur pour une utilisation dans les piles à combustible. Cette thèse s’inscrit dans ce projet avec pour but le développement de catalyseurs Fe/CeO2 et Cu/CeO2 déposés sur des supports de mousse céramique pour la réaction de conversion du gaz à l’eau à haute et basse températures, de manière à augmenter la production d’hydrogène et diminuer la perte de charge dans le système. Les principaux objectifs de la thèse sont la synthèse et les caractérisations des catalyseurs à base de fer et de cuivre, l’optimisation des conditions réactionnelles dans la limite du cadre fixé par le projet, la modélisation cinétique en présence des catalyseurs Fe/CeO2 et Cu/CeO2 et la transposition à grande échelle des catalyseurs pour une utilisation en réacteur pilote
The UNIfHY European project was launched in an optic of producing hydrogen from biomass to replace fossil fuels. Purification of gases produced by biomass gasification allows obtaining pure hydrogen which can be used in fuel cells. This thesis takes part in this project with the development of Fe/CeO2 and Cu/CeO2 catalysts deposited on ceramic foam supports for high temperature and low temperature water gas shift reaction to increase the production of hydrogen and decrease the pressure drop in the system. The main objectives of this thesis are the synthesis and characterizations of iron and copper based catalysts, the optimization of reaction conditions within the limits of the framework set by the project, the kinetic modeling of the reaction in the presence of Fe/CeO2 and Cu/CeO2 catalysts and the scale-up of catalysts to use them in a pilot reactor

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
Universidade Federal Fluminense. Instituto de Química. Programa de Pós-Graduação em Geociências-Geoquímica. Niterói, RJ
O presente trabalho buscou estimar a biomassa viva acima do solo (BVAS) em um fragmento florestal da Mata Atlântica localizado no sopé da Pedra de Itaocaia, município de Maricá/RJ. Para ajustar uma equação alométrica para a área de estudos, 7 indivíduos arbóreos representativos da região foram escalados e um galho de cada árvore foi retirado. Este procedimento possibilitou a obtenção de medidas dos volumes dos diferentes compartimentos arbóreos (tronco, galhos grossos, galhos finos e folhas) e das respectivas densidades básica (média=0,52 g/cm3) e fresca (média = 0,94 g/cm3), medidas estas utilizadas para calcular os fatores de forma dos galhos (FFG) e arbóreo (FFA). De maneira geral, as contribuições dos galhos finos e folhas decrescem com o aumento do diâmetro da base do galho, já a porcentagem de galhos grossos cresce e o valor do FFG diminui com o aumento do diâmetro da base do galho. A contribuição dos compartimentos galhos grossos, finos e folhas somam 33% da BVAS total arbórea na região. O FFA = 0,65 foi o fator que melhor estimou a BVAS por meio da equação alométrica BVAS = FFA*Db*AB*H, onde Db é a densidade básica, AB é a área basal e H é a altura da árvore. As estimativas de BVAS e estoque de carbono foram de 100 t/ha e 50,5 tC/ha, respectivamente, sugerindo que o fragmento florestal da Pedra de Itaocaia está num estágio de regeneração intermediário e com período de abandono estimado em 40 anos
This study aimed to estimate aboveground biomass (AGB) in an Atlantic Forest fragment located at the Stone Itaocaia, Marica, Rio de Janeiro. To fit an allometric equation for the study area, seven trees were scaled and a branch of each tree was removed. This procedure enabled to obtain measurements of the volumes of different compartments of trees (trunk, branches and leaves) and their basic densities (mean = 0.52 g/cm3) and cool (mean = 0.94 g / cm3), measures used to calculate the form factors of the branches (FFG) and the tree (FFA). In general, the contributions of branches and leaves decrease with increasing the diameter of the base of the branch, percentage of thick branches grow and FFG value decreases with increasing the diameter of the base of the branch. The contribution of branches, and leaves add 33% of the total tree AGB in the region. The FFA = 0.65 was the factor that best predicted the AGB by the allometric equation AGB = FFA * H * AB * Db, where Db is the density, AB is the basal area and H is the height of the tree. Estimates of carbon stock and AGB were 100 t / ha and 50.5 tC / ha, respectively, suggesting that the fragment of Stone Itaocaia is an intermediate stage of regeneration and abandonment period estimated at 40 years.

Tese de mestrado em Química Tecnológica, apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2015
Num futuro muito próximo, está previsto um aumento drástico das emissões de CO2 em todo o mundo. Segundo dados da OCDE, as emissões de CO2 aumentarão cerca de 50% até 2050. Um dos grandes contribuidores são as emissões de fontes energéticas como os combustíveis fósseis. Para além disso, é uma fonte não renovável de energia e de matéria-prima para a indústria química, o que tem levado muitos cientistas a tentarem encontrar novas fontes que sejam mais renováveis e ecológicas, como a biomassa. Segundo a Diretiva Europeia 28/2009/EC a biomassa “consiste na “fração biodegradável” de produtos, resíduos e detritos de origem biológica provenientes da agricultura (incluindo substâncias vegetais e animais), da exploração florestal e das indústrias afins, incluindo a da pesca e da aquicultura bem como a fração biodegradável de resíduos industriais e urbanos”. Aproximadamente 70% da biomassa vegetal é composta por células vegetais. É estimado que por ano são geradas cerca de 200x109 toneladas no mundo inteiro de biomassa, ultrapassando largamente a produção anual de barris de petróleo. Mesmo que se só vá utilizar uma fração da biomassa, esta pode apresentar uma boa alternativa ao petróleo na área energética mas também na área da produção de químicos. Um dos processos que tem sido alvo de desenvolvimento nos últimos tempos para a transformação da biomassa vegetal em produtos químicos é a liquefação. Este processo consiste na decomposição da celulose, hemicelulose e lenhina através duma reação de solvólise a temperaturas na ordem dos 160ºC e a pressão atmosférica. O produto final primário será uma mistura de polióis com funcionalidade cerca de 2,5, com alto valor OH e baixo valor ácido, o que os torna adequados para a produção de espumas rígidas de poliuretano. Neste trabalho polióis provenientes da casca de eucalipto (Eucalyptus Globulus), pinho (pinus pinaster), pó de cortiça e madeira de choupo foram diretamente introduzidos em formulações de espumas de um componente (One Component Foams, OCF) com o objetivo de substituir totalmente os polióis derivados do petróleo, criando um produto comerciável mais ecológico e proveniente de fontes renováveis. Deste modo, o trabalho dividiu-se em duas fases: uma em que se liquefez e caracterizou-se os polióis derivados das madeiras, e outra em que foram gradualmente introduzidos numa formulação base OCF já comerciável, verificando sempre as qualidades, envelhecimento e inflamabilidade das espumas obtidas. Na liquefação foram utilizados um monol e um diol como solventes. Depois de adicionados à biomassa dentro do reator, a temperatura foi elevada até 160 ºC e deixou-se reagir entre 1 e 2h, dependendo da biomassa. Depois de a liquefação ter ocorrido, os açúcares provenientes da celulose e hemicelulose são removidos através de extração liquido-liquido com água. A importância deste passo é elevada, pois se não forem removidos, o valor OH dos pólios será demasiado elevado e as espumas resultantes serão quebradiças. Para além disso, também é muito importante remover a maior quantidade de água possível dos polióis, pois uma elevada quantidade de água dentro das latas faz com que ocorra uma reação de expansão precoce e a pressão interna aumente, aumentando o risco de rebentamento. As quantidades utilizadas foram 70g para o pó de cortiça, 50 gramas para a casca de eucalipto e 85 gramas para a madeira de choupo, sendo os tempos de reação 2h, 1-2h e 1h-1h30min e as conversões 67-79%, 60-66% e 83-91%, respetivamente. As conversões da biomassa proveniente do eucalipto foram inferiores devido ao facto de esta ser uma casca, e portanto possuir um teor em lenhina substancialmente maior que as restantes. Os valores OH variaram entre 193 e 303 mg KOH/g e os conteúdos de água entre 0,35% e 1,07%. A análise do espectro de infravermelho permitiu concluir que o composto produzido é um álcool aromático com grupos carbonilo, provando assim ser um derivado da lenhina e da suberina. A introdução de cada um dos polióis provenientes da biomassa vegetal em formulações de espuma rígida de poliuretano de um componente foi feita de forma gradual, começando com 5%, 50% e por fim 100% em partes por peso, substituindo por fim completamente os polióis da formulação base. A substituição foi feita utilizando um ficheiro de excel existente na empresa, denominado de Foamcalc, onde os ajustes poderão ser feitos automaticamente. Depois de cada formulação estar pronta e devidamente ajustada, foram enchidas uma lata para cada poliól. No enchimento da lata três componentes gerais são adicionados: um componente A, composto por uma mistura dos polióis, catalisador, crosslinker, plastificante e surfactante; um componente B composto por um prepolímero de isocianato e um componente C composto por uma mistura de gases propulsores. O primeiro componente a adicionar à lata será o componente B. O prepolímero de isocianato é produzido in situ pela própria empresa utilizando um isocianato comercial. De seguida, é preparado o componente A adicionando todos os seus constituintes, tendo o cuidado de não adicionar primeiro os mais viscosos (para não colar no fundo) nem os de menor quantidade (para garantir que se integram completamente na mistura). De seguida, são misturados mecanicamente e adicionados à lata. Por fim a lata é selada e os gases são introduzidos através da válvula de saída, utilizando uma estação de enchimento adequada. Depois de agitar vigorosamente durante 1 minuto a lata é deixada a repousar durante 12h. Durante este período ocorre a reação de polimerização entre o poliól e o prepolímero de isocianato. Passado este tempo, é colocada em repouso novamente mas a 5ºC durante 4h, dando-se inicio depois aos testes de avaliação da espuma. Nos testes de avaliação, é determinada a taxa de débito, em g/s, e a espuma líquida é pulverizada em papel e em molde a 5 e 23ºC, onde é depois dada uma classificação de -5 a 5 a vários parâmetros visuais, como a quantidade de buracos presentes na base ou no interior da espuma curada. Uma espuma será qualificada como sendo de boa qualidade se a taxa de débito for superior a 3,5 g/s e se nenhum dos seus parâmetros tiver uma pontuação abaixo de 3. Nesta fase, as substituições até 100% foram efetuadas com sucesso em todos os polióis derivados da biomassa vegetal, e todas as espumas avaliadas nesta fase obtiveram uma classificação quase boa, sendo a baseada no poliól de pinho a melhor com apenas um valor abaixo de 3 na substituição a 100%, sendo melhor até que uma espuma de controlo baseada num poliól derivado do caju. Visto que a introdução foi um sucesso, o teste de envelhecimento acelerado foi realizado em todas as formulações. Neste teste a qualidade da espuma é avaliada a 0, 6 e 12 meses, por isso foram produzidas 3 latas por cada formulação, incluindo a de controlo. Uma lata foi logo avaliada no dia seguinte, e as outras duas foram colocadas numa estufa a 45ºC durante 26 e 52 dias, de modo a obter um envelhecimento acelerado de 6 e 12 meses, respetivamente. Passado esse tempo, as espumas foram avaliadas utilizando o mesmo método referido anteriormente e a deterioração de qualidade foi avaliada. Ao contrário da fase anterior, as espumas que apresentaram melhor resultado foram as baseadas nos polióis derivados do pó de cortiça. Para uma espuma ser comerciável, não só terá que passar no teste de qualidade, mas também terá que ser B2 (não muito inflamável) e possuir menos de 1% de monomérico livre. Deste modo, testes de resistência à chama foram realizados de acordo com a parte 1 da norma DIN-4102, utilizando as formulações com 100% polióis derivados da biomassa vegetal mas com 5g de retardante de chama. Contudo, os resultados foram negativos em todas as formulações, incluindo a formulação base e a de controlo. A percentagem de monomérico livre foi impossível de determinar devido ao facto de não haver equipamento disponível na altura. Em suma, a introdução dos polióis derivados da biomassa foi um sucesso, produzindo espumas com qualidade quase boa e que não deterioram muito ao longo do tempo. Porém, como trabalho futuro será necessário melhorar as formulações, realizar estudos de resistência à chama com novos e variados retardantes de chama e medir a percentagem de monomérico livre de modo a que se tornem comerciáveis.
Fossil fuels, such as natural gas, coal and oil are the base of all modern societies. They are used to produce energy that fuels all kind of industries and generates electricity. According to the OECD environmental outlook, the emissions are expected to grow 50% between now and until 2050, primarily due to a 70% growth in energy-related CO2 emissions. In Europe, the chemical industry accounted for 14% of total greenhouse emissions in 1990.6 In an effort to tackle this global problem, efforts are being made by the chemical companies by developing more ecological products. One alternative carbon source to the fossil fuels is the production of multifunctional polyols from the plant biomass by a solvolysis liquefaction process. In this work, polyols were successfully produced by an acid liquefaction of eucalyptus bark, pine wood chips, cork powder and poplar wood chips, at 160ºC and an ambient pressure, with conversion ratios of 58-91%, depending on the biomass. These new polyols, or lignopolyols, had an OH value of 193-303 mg KOH/g and a water content of 0,31-1,07%. The infrared spectra analysis concluded that they were an aromatic compound, with carbonyl and OH groups, which led to the conclusion that they must be derived from lignin and suberin. After they were produced, the polyols from a base OCF formulation were progressively replaced by the lignopolyols in 5, 50 and then 100% parts per weight. The resultant rigid polyurethane foams had good outputs (over 3,5 g/s), an overall almost good quality and low quality degradation after 12 months of shelf life. The foam that presented the best results was the one based on the cork lignopolyol, having better quality than the control foam. However, all of them were very flammable submitted to an ignitibility test, even when a flame retardant was used. To turn them into commercially viable one component foams, improvements in the formulations and further tests shall be done in future work. Flame retardant tests and the measurement of free monomeric MDI with HPLC shall be carried out.