Orientador: João Cláudio Thoméo / Banca: José Teixeira Freire / Banca: Maria Aparecida Mauro / Resumo: O propósito deste trabalho foi obter parâmetros físicos e térmicos para simulação de reatores de leito fixo para fermentação em estado sólido (FES), empregando rejeitos sólidos agroindustriais como substratos e fungos como agentes fermentativos. Os materiais estudados foram bagaço de cana, resíduo agroindustrial comumente empregado na FES, e um meio composto por bagaços de cana e laranja e farelo de trigo na proporção 1:2:2 (p/p), substrato empregado para obtenção de enzimas pectinolíticas por FES. Foi determinada a condutividade térmica na estagnação (K0) pelo método da sonda linear. Observou-se que a condutividade era muito baixa para os recheios secos (inferior a 0,1 W/mºC), mas aumentava bruscamente para recheios muito úmidos (atingindo 0,5 W/mºC), o que foi atribuído à condução de calor através da água. Também foram determinados os parâmetros térmicos dos leitos percolados por ar com baixas vazões, típicas da FES. Os valores da condutividade térmica efetiva radial (Kr) obtidos foram muito baixos, tendendo ao valor da estagnação, e os valores do coeficiente convectivo de transferência de calor parede-fluido (hp) foram muito inferiores aos encontrados na literatura, devido às baixas vazões de ar. Foram desenvolvidos programas para aquisição de dados experimentais de temperatura por meio do software de interface gráfica LabView (National Instruments). Também foram desenvolvidos programas em MatLab para cálculo dos parâmetros térmicos dos sistemas, tanto para o modelo unidimensional (coeficiente global U) quanto para o bidimensional. Esses programas permitiram calcular os parâmetros térmicos imediatamente após aquisição dos dados do processo. Programas de simulação numérica foram desenvolvidos em MatLab para simular o crescimento do fungo termofílico Thermomucor indicae seudaticae N31 e o comportamento térmico do processo de FES... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The purpose of this work was to get physical and thermal parameters for simulation of reactors of fixed packed beds percolated by air for solid state fermentation (SSF), using agro- industrial solid residues as substrata and molds as fermentative agents. The materials studied were sugar cane bagasse, agro-industrial residue commonly used in SSF, and a medium composed by sugar cane and orange bagasses and wheat bran in ratio 1:2:2 (w/w), substratum used for pectinolitics enzymes attainment for SSF. The thermal conductivity on stagnation (K0) was determined by heating linear method. It was observed that the conductivity was very low for dried materials (below 0,1 W/mºC), but increased brusquely for very humid materials (reaching 0,5 W/mºC), what it was admitted to be due to conduction of heat through the water. Also the thermal parameters of the fixed packed beds percolated by air with low outflows, typical of SSF, had been determined. The values of the thermal conductivity radial effective (Kr) gotten had been very low, tending to the value of the stagnation, and the values of the convective coefficient of heat transfer wall-fluid (hp) had been very below to the found on literature, which had to the low air outflows. Programs for acquisition of experimental data of temperature by means of the software of graphical interface LabView had been developed (National Instruments). Also programs in MatLab for calculation of the thermal parameters of the systems had been developed, as much for the one-dimensional model (global coefficient U) how much for the two-dimensional. These programs had allowed calculating the thermal parameters immediately after acquisition of the data of the process. Programs of numerical simulation had been developed in MatLab to simulate the growth of thermopile mold Thermomucor indicae seudaticae N31 and the thermal behavior of the process of SSF lead by Umsza Guez... (Complete abstract click electronic access below) / Mestre

A ciclodextrina glicosiltransferase (CGTase) é a única enzima capaz de catalisar a reação de ciclização a partir do amido e, assim, formar oligossacarídeos cíclicos conhecidos como ciclodextrinas (CDs). Através desta reação é produzida uma mistura de α-, β- e γ-CD que, respectivamente, contém 6, 7 e 8 resíduos de glicose. As CDs têm atraído enorme atenção devido ao seu grande potencial de aplicação em diversas áreas da indústria. Potencial este proporcionado por sua estrutura cônica, com interior hidrofóbico, capaz de encapsular sólidos, líquidos e gases, conferindo propriedades importantes e protegendo-os. Neste trabalho foi estudada a imobilização de uma CGTase em sílica mesoporosa de forma direcionada às cisteínas presentes em sua superfície, alterando a exposição do sítio ativo. A ligação via cisteínas nativas da proteína aumentou em quatro vezes a eficiência da imobilização, quando comparada a ligação via grupamento amino. Esta, no entanto, apresentou maior atividade enzimática em faixas mais amplas de temperatura e pH, além de maior estabilidade operacional, mantendo 100 % de sua atividade após 200 h de reação contínua a 60 °C e pH 4. Ainda que apresentando menor estabilidade da ligação, o derivado obtido por ligação dissulfeto manteve 40 % da atividade inicial durante 200 h e então, o suporte pôde ser recarregado e reutilizado por igual período. Os suportes desenvolvidos apresentaram estabilidade satisfatória, possibilitando o uso do derivado imobilizado em reator de leito fixo operado de forma contínua. Quando avaliado em relação a produção das três ciclodextrinas principais, o derivado cuja imobilização da enzima ocorreu via grupamento amino, evidenciou a possibilidade de modulação da produção apenas variando as condições de reação. α- e β-CD foram produzidas preferencialmente em pH 8,0 e 2 min (3,44 mg mL-1 e 3,51 mg mL-1, respectivamente), enquanto que pH mais ácido (4,0) e maior tempo de reação (141 min) favoreceram a formação de γ-CD (3,35 mg mL-1), com baixa formação α-CD (0,75 mg mL-1). Por fim, os resultados deste estudo evidenciam a importância da imobilização da CGTase para a estabilização de sua estrutura a fim de aplicá-la em sistemas contínuos de produção de CDs onde é possível modular o perfil dos produtos gerados em função das condições de reação, aumentando assim a produtividade do biocatalisador. / Cyclodextrin glycosyltransferase (CGTase) is the only enzyme capable of catalyzing the cyclization reaction from the starch and thus forming cyclic oligosaccharides known as cyclodextrins (CDs). Through this reaction, is produced a mixture of α-, β- and γ-CD containing, 6, 7 and 8 glucose residues respectively. Cyclodextrins (CD) have been attracting considerable attention because of its great potential for application in various areas of industry. This potential is provided by its conical structure with hydrophobic interior, capable of encapsulating solids, liquids and gases, changing important features and protecting them. In this work, the immobilization of CGTase in mesoporous silica was studied in a way directed to cysteines present on its surface, altering the exposure of the active site. The connection via native cysteine of the protein increased by four times the efficiency of immobilization compared to amino groups connection. The binding of amino groups, however, showed greater enzymatic activity in wider ranges of temperature and pH, and higher operational stability, while maintaining 100 % of its activity after 200 h of continuous reaction at 60 °C and pH 4. Although showing less stable connection, the derivative obtained by disulfide bond retained 40 % of the initial activity for 200 h and then, the support could be reloaded and reused for the same period. Developed supports showed satisfactory stability, enabling the use of the derivative assets in a packed bed reactor and operated continuously. It was demonstrated the possibility of modulating the CDs production just varying the reaction conditions, using the derivative of which the enzyme immobilization occurred via amino group, to evaluate the production of three main cyclodextrins. α- and β-CD were produced preferentially at pH 8.0 and 2 min (3.44 mg mL-1 and 3.51 mg mL-1, respectively), whereas the more acid pH (4.0) and longer reaction (141 min) favored the formation of γ-CD (3.35 mg mL-1 and 0.75 mg mL-1 of α-CD). Finally, the results of this study show the importance of the immobilization of CGTase to the stabilization of its structure in order to apply it in continuous CD production systems, where it is possible to modulate the profile of the products generated as a function of the reaction conditions, thus increasing the productivity of the biocatalyst.

Biodiesel is the most successful drop-in biofuel used in transportation. It can reduce GHG emissions in transportation by 50 to 90% depending on the type of feedstock used. Waste cooking oils and fats containing free fatty acids (FFA) are less expensive feedstocks for biodiesel production than refined vegetable oils. The major issue that limits the use of these oils as feedstock is the interference of FFAs with widely used base catalyzed reaction processes. The FFAs consume base catalyst, produce water of neutralization and form soaps that create emulsions downstream in the process reducing process yields. There is an important need to develop technologies that reduce the FFA content in these oils to below 0.5 wt%; the accepted limit for a feedstock to be processed by the base catalysed reaction. Enzymes are an efficient and environmentally friendly catalyst for FFA esterification. However, they are prone to deactivation with methanol and also catalyze the hydrolysis of esters and triglycerides to FFA. Using them to pre-treat oils and fats remains a challenge: in the presence of water, enzymes can readily produce FFAs from lipids. The objective of this work was to investigate two enzymatic processes to pre-treat acidic oil below the FFA requirement of 0.5 wt%. In this study, two different continuous systems, a packed bed reactor (PBR) and membrane reactor (MR) were used in FFA enzymatic esterification to meet the 0.5 wt% requirement, improve the reusability of enzymes and reduce catalyst cost. The esterification in the PBR was carried out using CALB immobilized on a new 2D/3D nanoplatelet support (TAN). The enzyme was covalently bonded to the TAN using a hydrophobic epoxy ligand. Acidic oil containing canola oil and 2.5 wt% FFA was used as the feedstock for the esterification. It was found that the FFA concentration met the quality specification of <0.5 wt% using CALB-TAN, while it did not using the commercial Novozym 435. The surface fluid velocity was found to have an effect on the removal of water from the PBR reactor. When the velocity was too low, water was retained in the reactor and the FFA conversion was low, when it was too high the reaction time for esterification was not sufficient. It was found that feed velocity of 3 to 6 x 10-5 m/s met the 0.5 wt% requirement. In the PBR, the use of CALB-TAN successfully eliminated the hydrolysis of TG and achieved the continuous esterification of FFA for 42 days. In the MR, acidic oil containing canola oil and 10 wt% FFA was used as the feedstock for the esterification. The enzyme adsorbed on the surface of the polar phase containing glycerol and water and was successfully retained in the reactor by a 0.2-micron ceramic membrane. The addition of glycerol increased the polarity of the dispersed phase in the reactor, bounded water, and retained the liquid enzyme in the reactor. However, the added glycerol in the reactor increased the operating pressure of the reactor. The operating pressure was reduced by adding biodiesel to the feedstock prior to treatment. The lowest level of FFA from the 10 wt% FFA feedstock was 0.68 wt%. This would require a second polishing step to reach the required 0.5 wt%. The PBR and MR using CALB are technologies that limit the hydrolysis at low FFA concentrations and are promising for the pre-treatment of acidic feedstocks in base catalysed biodiesel processes.

A ciclodextrina glicosiltransferase (CGTase) é a única enzima capaz de catalisar a reação de ciclização a partir do amido e, assim, formar oligossacarídeos cíclicos conhecidos como ciclodextrinas (CDs). Através desta reação é produzida uma mistura de α-, β- e γ-CD que, respectivamente, contém 6, 7 e 8 resíduos de glicose. As CDs têm atraído enorme atenção devido ao seu grande potencial de aplicação em diversas áreas da indústria. Potencial este proporcionado por sua estrutura cônica, com interior hidrofóbico, capaz de encapsular sólidos, líquidos e gases, conferindo propriedades importantes e protegendo-os. Neste trabalho foi estudada a imobilização de uma CGTase em sílica mesoporosa de forma direcionada às cisteínas presentes em sua superfície, alterando a exposição do sítio ativo. A ligação via cisteínas nativas da proteína aumentou em quatro vezes a eficiência da imobilização, quando comparada a ligação via grupamento amino. Esta, no entanto, apresentou maior atividade enzimática em faixas mais amplas de temperatura e pH, além de maior estabilidade operacional, mantendo 100 % de sua atividade após 200 h de reação contínua a 60 °C e pH 4. Ainda que apresentando menor estabilidade da ligação, o derivado obtido por ligação dissulfeto manteve 40 % da atividade inicial durante 200 h e então, o suporte pôde ser recarregado e reutilizado por igual período. Os suportes desenvolvidos apresentaram estabilidade satisfatória, possibilitando o uso do derivado imobilizado em reator de leito fixo operado de forma contínua. Quando avaliado em relação a produção das três ciclodextrinas principais, o derivado cuja imobilização da enzima ocorreu via grupamento amino, evidenciou a possibilidade de modulação da produção apenas variando as condições de reação. α- e β-CD foram produzidas preferencialmente em pH 8,0 e 2 min (3,44 mg mL-1 e 3,51 mg mL-1, respectivamente), enquanto que pH mais ácido (4,0) e maior tempo de reação (141 min) favoreceram a formação de γ-CD (3,35 mg mL-1), com baixa formação α-CD (0,75 mg mL-1). Por fim, os resultados deste estudo evidenciam a importância da imobilização da CGTase para a estabilização de sua estrutura a fim de aplicá-la em sistemas contínuos de produção de CDs onde é possível modular o perfil dos produtos gerados em função das condições de reação, aumentando assim a produtividade do biocatalisador. / Cyclodextrin glycosyltransferase (CGTase) is the only enzyme capable of catalyzing the cyclization reaction from the starch and thus forming cyclic oligosaccharides known as cyclodextrins (CDs). Through this reaction, is produced a mixture of α-, β- and γ-CD containing, 6, 7 and 8 glucose residues respectively. Cyclodextrins (CD) have been attracting considerable attention because of its great potential for application in various areas of industry. This potential is provided by its conical structure with hydrophobic interior, capable of encapsulating solids, liquids and gases, changing important features and protecting them. In this work, the immobilization of CGTase in mesoporous silica was studied in a way directed to cysteines present on its surface, altering the exposure of the active site. The connection via native cysteine of the protein increased by four times the efficiency of immobilization compared to amino groups connection. The binding of amino groups, however, showed greater enzymatic activity in wider ranges of temperature and pH, and higher operational stability, while maintaining 100 % of its activity after 200 h of continuous reaction at 60 °C and pH 4. Although showing less stable connection, the derivative obtained by disulfide bond retained 40 % of the initial activity for 200 h and then, the support could be reloaded and reused for the same period. Developed supports showed satisfactory stability, enabling the use of the derivative assets in a packed bed reactor and operated continuously. It was demonstrated the possibility of modulating the CDs production just varying the reaction conditions, using the derivative of which the enzyme immobilization occurred via amino group, to evaluate the production of three main cyclodextrins. α- and β-CD were produced preferentially at pH 8.0 and 2 min (3.44 mg mL-1 and 3.51 mg mL-1, respectively), whereas the more acid pH (4.0) and longer reaction (141 min) favored the formation of γ-CD (3.35 mg mL-1 and 0.75 mg mL-1 of α-CD). Finally, the results of this study show the importance of the immobilization of CGTase to the stabilization of its structure in order to apply it in continuous CD production systems, where it is possible to modulate the profile of the products generated as a function of the reaction conditions, thus increasing the productivity of the biocatalyst.

abstract: Arsenic (As) is a naturally occurring element that poses a health risk when continually consumed at levels exceeding the Environmental Protection Agencies (EPA) maximum contaminant level (MCL) of 10 ppb. With the Arizona Department of Water Resources considering reliance on other sources of water other than just solely surface water, groundwater proves a reliable, supplemental source. The Salt River Project (SRP) wants to effectively treat their noncompliance groundwater sources to meet EPA compliance. Rapid small-scale column tests (RSSCTs) of two SRP controlled groundwater wells along the Eastern Canal and Consolidated Canal were designed to assist SRP in selection and future design of full-scale packed bed adsorbent media. Main concerns for column choice is effectiveness, design space at groundwater wells, and simplicity. Two adsorbent media types were tested for effective treatment of As to below the MCL: a synthetic iron oxide, Bayoxide E33, and a strong base anion exchange resin, SBG-1. Both media have high affinity toward As and prove effective at treating As from these groundwater sources. Bayoxide E33 RSSCT performance indicated that As treatment lasted to near 60,000 bed volumes (BV) in both water sources and still showed As adsorption extending past this operation ranging from several months to a year. SBG-1 RSSCT performance indicated As, treatment lasted to 500 BV, with the added benefit of being regenerated. At 5%, 13%, and 25% brine regeneration concentrations, regeneration showed that 5% brine is effective, yet would complicate overall design and footprint. Bayoxide E33 was selected as the best adsorbent media for SRP use in full-scale columns at groundwater wells due to its simplistic design and high efficiency. / Dissertation/Thesis / Masters Thesis Civil and Environmental Engineering 2015

Made available in DSpace on 2014-06-11T19:24:45Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-28Bitstream added on 2014-06-13T18:21:12Z : No. of bitstreams: 1 casciatori_fp_me_sjrp_parcial.pdf: 81692 bytes, checksum: 8909085df78fb65d202e35e91ecbb5b2 (MD5) Bitstreams deleted on 2015-08-28T16:08:54Z: casciatori_fp_me_sjrp_parcial.pdf,. Added 1 bitstream(s) on 2015-08-28T16:09:59Z : No. of bitstreams: 1 000640118.pdf: 1821375 bytes, checksum: 2ac04413db80f0e987e207401ed80680 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O propósito deste trabalho foi obter parâmetros físicos e térmicos para simulação de reatores de leito fixo para fermentação em estado sólido (FES), empregando rejeitos sólidos agroindustriais como substratos e fungos como agentes fermentativos. Os materiais estudados foram bagaço de cana, resíduo agroindustrial comumente empregado na FES, e um meio composto por bagaços de cana e laranja e farelo de trigo na proporção 1:2:2 (p/p), substrato empregado para obtenção de enzimas pectinolíticas por FES. Foi determinada a condutividade térmica na estagnação (K0) pelo método da sonda linear. Observou-se que a condutividade era muito baixa para os recheios secos (inferior a 0,1 W/mºC), mas aumentava bruscamente para recheios muito úmidos (atingindo 0,5 W/mºC), o que foi atribuído à condução de calor através da água. Também foram determinados os parâmetros térmicos dos leitos percolados por ar com baixas vazões, típicas da FES. Os valores da condutividade térmica efetiva radial (Kr) obtidos foram muito baixos, tendendo ao valor da estagnação, e os valores do coeficiente convectivo de transferência de calor parede-fluido (hp) foram muito inferiores aos encontrados na literatura, devido às baixas vazões de ar. Foram desenvolvidos programas para aquisição de dados experimentais de temperatura por meio do software de interface gráfica LabView (National Instruments). Também foram desenvolvidos programas em MatLab para cálculo dos parâmetros térmicos dos sistemas, tanto para o modelo unidimensional (coeficiente global U) quanto para o bidimensional. Esses programas permitiram calcular os parâmetros térmicos imediatamente após aquisição dos dados do processo. Programas de simulação numérica foram desenvolvidos em MatLab para simular o crescimento do fungo termofílico Thermomucor indicae seudaticae N31 e o comportamento térmico do processo de FES... / The purpose of this work was to get physical and thermal parameters for simulation of reactors of fixed packed beds percolated by air for solid state fermentation (SSF), using agro- industrial solid residues as substrata and molds as fermentative agents. The materials studied were sugar cane bagasse, agro-industrial residue commonly used in SSF, and a medium composed by sugar cane and orange bagasses and wheat bran in ratio 1:2:2 (w/w), substratum used for pectinolitics enzymes attainment for SSF. The thermal conductivity on stagnation (K0) was determined by heating linear method. It was observed that the conductivity was very low for dried materials (below 0,1 W/mºC), but increased brusquely for very humid materials (reaching 0,5 W/mºC), what it was admitted to be due to conduction of heat through the water. Also the thermal parameters of the fixed packed beds percolated by air with low outflows, typical of SSF, had been determined. The values of the thermal conductivity radial effective (Kr) gotten had been very low, tending to the value of the stagnation, and the values of the convective coefficient of heat transfer wall-fluid (hp) had been very below to the found on literature, which had to the low air outflows. Programs for acquisition of experimental data of temperature by means of the software of graphical interface LabView had been developed (National Instruments). Also programs in MatLab for calculation of the thermal parameters of the systems had been developed, as much for the one-dimensional model (global coefficient U) how much for the two-dimensional. These programs had allowed calculating the thermal parameters immediately after acquisition of the data of the process. Programs of numerical simulation had been developed in MatLab to simulate the growth of thermopile mold Thermomucor indicae seudaticae N31 and the thermal behavior of the process of SSF lead by Umsza Guez... (Complete abstract click electronic access below)

Thesis submitted in fulfilment of the requirements for the degree of Masters of Technology: Chemical Engineering in the Faculty of Engineering Cape Peninsula University of Technology, South Africa Supervisor: Prof TV Ojumu Cape Town Campus September 2013 / Jarosite formation is regarded as undesirable in the bioleaching processes as it depletes ferric reagent; a critical reagent for the oxidation of most sulphide minerals, from bioleach solution. It creates kinetic barriers and clogs on mineral surfaces, thereby retarding leach rates of most minerals. However, jarosite has also been shown to serve as support for the attachment of bioleaching microbes, facilitating a high ferric-iron generation rate. In this study, a series of experiments on microbial ferrous-iron oxidation by a mesophilic microbe were carried out in a novel packed-column bioreactor with a view to investigating the potential use of solution pH to manage jarosite accumulation in the bioreactor. The kinetics of the oxidation was also investigated to establish base case data for the novel bioreactor. The bioreactor was packed with glass balls 15 mm in diameter. The experiments were conducted at a constant temperature of 38.6 °C, residence time of 18 hrs, airflow rate of 20 mL.s-1 and at desired solution pHs (1.3, 1.5 and 1.7). The results showed that the amount of jarosite accumulation is proportional to the operating solution pH and also to the duration of operation of the bioreactor. Jarosite precipitate of 4.95, 5.89 and 7.08 g.L-1 were obtained after 10 days of continuous operation at solution pH of 1.3, 1.5 and 1.7 respectively, while after 15 days the precipitate concentration increased to 5.50, 7.90 and 9.98 g.L-1respectively. The results also showed that a 33% and 52% reduction in jarosite accumulation could be achieved by a gradual decrease of the bioreactor solution pH after being continuously operated for 10 days from pH 1.7 to 1.5 and pH 1.7 to 1.3, respectively, for an additional five days of continuous operation. The results of the ferrous-iron biooxidation kinetics investigated at pH 1.3 show a maximum ferrous oxidation rate ( max 2 Fe r ) of 6.85 mmol.L-1.h-1 and apparent affinity kinetics constants (   2 Fe K , 2 Fe K ) of 0.001 mmol Fe2+.L-1 and 0.006 (dimensionless) using Hansford and Monod equations, respectively. Although a direct relationship exists between jarosite formation and solution pH, the results of this study may be relevant in bioleach heaps, or at least in column bioreactors, to manage and control jarosite accumulation, thereby improving leach kinetics of sulphide minerals.

Thesis submitted in fulfilment of the requirements for the degree of Masters of Technology: Chemical Engineering in the Faculty of Engineering Cape Peninsula University of Technology, South Africa, 2013 / Jarosite formation is regarded as undesirable in the bioleaching processes as it depletes ferric reagent; a critical reagent for the oxidation of most sulphide minerals, from bioleach solution. It creates kinetic barriers and clogs on mineral surfaces, thereby retarding leach rates of most minerals. However, jarosite has also been shown to serve as support for the attachment of bioleaching microbes, facilitating a high ferric-iron generation rate. In this study, a series of experiments on microbial ferrous-iron oxidation by a mesophilic microbe were carried out in a novel packed-column bioreactor with a view to investigating the potential use of solution pH to manage jarosite accumulation in the bioreactor. The kinetics of the oxidation was also investigated to establish base case data for the novel bioreactor. The bioreactor was packed with glass balls 15 mm in diameter. The experiments were conducted at a constant temperature of 38.6 °C, residence time of 18 hrs, airflow rate of 20 mL.s-1 and at desired solution pHs (1.3, 1.5 and 1.7). The results showed that the amount of jarosite accumulation is proportional to the operating solution pH and also to the duration of operation of the bioreactor. Jarosite precipitate of 4.95, 5.89 and 7.08 g.L-1 were obtained after 10 days of continuous operation at solution pH of 1.3, 1.5 and 1.7 respectively, while after 15 days the precipitate concentration increased to 5.50, 7.90 and 9.98 g.L-1respectively. The results also showed that a 33% and 52% reduction in jarosite accumulation could be achieved by a gradual decrease of the bioreactor solution pH after being continuously operated for 10 days from pH 1.7 to 1.5 and pH 1.7 to 1.3, respectively, for an additional five days of continuous operation. The results of the ferrous-iron biooxidation kinetics investigated at pH 1.3 show a maximum ferrous oxidation rate ( max 2 Fe r ) of 6.85 mmol.L-1.h-1 and apparent affinity kinetics constants (   2 Fe K , 2 Fe K ) of 0.001 mmol Fe2+.L-1 and 0.006 (dimensionless) using Hansford and Monod equations, respectively. Although a direct relationship exists between jarosite formation and solution pH, the results of this study may be relevant in bioleach heaps, or at least in column bioreactors, to manage and control jarosite accumulation, thereby improving leach kinetics of sulphide minerals.

Orientador: Oswaldo Durival Rossi Junior / Banca: Luiz Augusto do Amaral / Banca: Ana Maria Centola Vidal Martins / Resumo: A deterioração "blown pack" é caracterizada por abundante produção de gás, induzindo a completa distensão da embalagem durante o processo de estocagem sob refrigeração. Quando a embalagem é aberta, há um odor desagradável, levemente fecal. O gás presente na embalagem é composto por dióxido de carbono e hidrogênio e por vários tipos butíricos do metabolismo fermentativo. O objetivo deste experimento foi determinar possíveis causadores deste tipo de deterioração, quantificando as populações de bactérias da família Enterobacteriaceae, e caracterizando-as nos principais gêneros e espécies encontradas, o número de bactérias ácido-lácticas, a freqüência de Clostridium estertheticum e do Clostridium gasigenes, em carnes próprias para o consumo e em carnes que apresentaram a deterioração "blown pack". Para contagem e identificação dos membros da família Enterobacteriaceae e contagem de bactérias ácido-lácticas utilizou-se de técnicas microbiológicas clássicas. Já para pesquisa do C. estertheticum e C. gasigenes fez-se uso de técnicas de biologia molecular. Os microrganismos da família Enterobacteriaceae e bactérias ácido-láticas estavam presentes em populações elevadas e em maior número nas carnes com deterioração "blown pack". A espécie mais freqüentemente encontrada foi a Hafnia alvei. As amostras com deterioração "blown pack' apresentaram maior positividade para o C. estertethicum que amostras não deterioradas. Não houve diferença estatística de positividade para a presença do C. gasigenes entre amostras com deterioração "blown pack" e carnes não deterioradas. A principal forma de controle desta deterioração é a prevenção da contaminação da carne por material fecal. / Abstract: The "blown pack" spoilage is characterised by abundant gas production, leading to complete gross distention pack during refrigerated storage. When the packaging is opened, there is an unpleasant smell, lightly fecal. The gas present in the package is composed of carbon dioxide and hydrogen and also of several butyric types of metabolism fermentation. The purpose of this experiment was to determine possible causes of this spoilage type, quantifying the populations of bacteria of the family Enterobacteriaceae, and characterizing them in the major genera and species found, the number of lactic acid bacteria, the frequency of Clostridium estertheticum and Clostridium gasigenes in meat proper for consumption and meat which showed the "blown pack" spoilage. In order to enumerate and identify the members of the Enterobacteriaceae family, and to enumerate the lactic acid bacteria the procedure was classical microbiological techniques. However to search the C. estertheticum and C. gasigenes the procedure was molecular biology techniques. The microorganisms of the family Enterobacteriaceae and lactic acid bacteria were present in large populations and in greater numbers in meat with "blown pack" spoilage. The species which were found more often was the Hafnia alvei. Samples of "blown pack" spoilage had greater positive features for C. estertethicum than samples not damaged. There was no statistical difference of positive features for the presence of C. gasigenes between samples of "blown pack" spoilage and not damaged meat. The main way to control this spoilage is the prevention of contamination of meat by fecal material. / Mestre

Orientadores: Teresa Massako Kakuta Ravagnani, João Alexandre Ferreira da Rocha Pereira / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-05T04:47:12Z (GMT). No. of bitstreams: 1 Lang_JeanPierre_M.pdf: 1967050 bytes, checksum: 0383f4c0388e6e7aa19f19c4c4688052 (MD5) Previous issue date: 2005 / Resumo: As colunas de recheio são equipamentos intensamente aplicados em operações de separação tais como destilação, absorção de dessorção. No entanto, a sua capacidade à transferência de massa em contracorrente é limitada devido à sua inundação. Uma nova tecnologia HIGEE ('high g¿ ¿ alta gravidade é proposta para superar esta limitação. Uma cluna HIGEE utiliza um recheio rotativo que induz acelerações centrífugas acima de 1000 vezes a aceleração da gravidade terrestre. O aumento da força motriz permite o aumento da capacidade e da eficiência da coluna. De acordo com vários autores, o tamanho do equipamento fica consideravelmente reduzido, apresentando vantagens econômicas e operacionais. A principal proposta deste trabalho é avaliar a forma como a coluna com recheio rotatico se comporta quando o raio externo do rotos é aumentado de 8 (Nascimento, 1999 e 2003) para 13cm.Os experimentos foram conduzidos em condições de refluxo total, sendo utilizando dois sistemas destilantes: n-hexano/n-heptano e etanol/água. A velocidade do rotor foi variada de 500 a 2300 rpm, criando acelerações contrifugas de 26 a256 vezes a aceleração da gravidade. O efeito da vazão de vapor, velocidade de rotação e do sistema destilante sobre o coeficiente de transferência de massa, 'K IND. y¿¿a IND. e¿ depende do fluxo de vapor, mas fracamente da velocidade do rotor...Observação: O resumo, na íntegra, poderá ser visualizado no texto completo da tese digital / Abstract: Packed colummns are equipment intensively applied in separations such as distillation, absorption and stripping , absorption and strippig. However, its for counter-current mass transfer is limited due to its flooding. A new HIGEE (high g ¿ high gravity) technology is proposal to overlap this limitation. A HIGEE column uses a rotating machine that promotes centrifugal accelerations above 1000 times the terrestrial gravity acceleration. The increase of the driving force allows the increase of column¿s capacity and efficiency. In accordance with some authors, the equipment size considerably reduced presenting economic and operational advantages. The main proposal of this work is to evaluate how the mass transfer behavior of the HIGEE column changes when the external rotor radius is increased from 8 (Nascimento 1999 and 2003) to 13 cm. The experiments had been conduced in total reflux conditions using two distilling system n-hexane/n-heptane and ethanol/ water. The rotor's speed was vaied from 500 to 2300 rpm , provided centrifugal accelerations from 26 to 556 times higher than terrestrial gravity acceleration. The effect of the vapor outflow, rotation speed and distilling system on mass transfer coefficient 'K IND. y¿¿a IND. e¿ and transfer unit area, 'AUT IND. G¿had been analyzed for each rotor size...Note: The complete abstract is available with the full electronic digital thesis or dissertations / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química