<p> The temperature policy with time is sought which maximizes a performance index for a fixed time in a tubular reactor with uniform temperature, decaying catalyst, and two first-order irreversible parallel reactions. </p> <p> For the case where the performance index is the total amount of desired product produced, an analogy between the optimization problems for a first-order reversible reaction and a parallel reaction first-order in both. paths is developed. </p> <p> A numerical procedure together with theoretical developments is used to solve the problem for a more general performance index which takes into account the cost of the reactant as well as the value of the desired product. The problem is· treated in the format of Pontryagin's Maximum Principle. </p> / Thesis / Master of Engineering (MEngr)

The aim is to study a continuous chemical process, and then analyze the hold process of the reactor and build the models which could be trained to realize the fault diagnosis and localization in the process. An experimental system has been built to be the research base. That includes experiment part and record system. To the diagnosis and localization methods, the work presented the methods with the data-based approach, mainly the Bayesian network and RBF network based on GAAPA (Genetic Algorithm with Auto-adapted of Partial Adjustment). The data collected from the experimental system are used to train and test the models.

<p> The optimal temperature and catalyst renewal policies which maximize the average profit over a free time period in a tubular reactor with uniform temperature and decaying catalyst for a single irreversible reaction, are sought.</p> <p> In addition, the optimal initial catalyst activity and the optimal total time have been studied.</p> <p> A numerical procedure together with theoretical developments is used to solve the problem for a more general performance index (average profit function) which takes into account the value of the desired product, the cost for the regeneration of the catalyst and the cost of the fresh catalyst.</p> <p> The problem is treated in the format of Pontryagin's Maximum Principle.</p> / Thesis / Master of Engineering (MEngr)

A digestão anaeróbia termofílica é uma opção vantajosa para efluentes descartados a altas temperaturas, além de estimular rotas mais eficientes de produção de H2. No entanto, os resultados da literatura divergem bastante, os rendimentos de H2 são inferiores ao valor teórico possível e poucos estudos avaliaram diferentes configurações para indicar a mais eficiente. Assim, este estudo avaliou a produção de H2 a partir da sacarose em três tipos de reator: reator anaeróbio de fluxo ascendente e manta de lodo (UASB), reator tubular de fluxo ascendente com leito empacotado (TCS) e sem material suporte (TSS), operados a 55°C. Os tempos de detenção hidráulica (TDH) aplicados ao reator UASB foram 12, 6 e 2 h e aos reatores TCS e TSS foram 2 e 0,5 h. Pré-tratamento térmico (100°C por 15 min) foi aplicado ao inóculo metanogênico do UASB e TCS e TSS foram auto inoculados. O efeito de nutrientes e a concentração nutricional ótima para a produção de H2 foram investigados através de ensaios em batelada. Com TDH de 2 h, o material suporte afetou a transferência de massa, resultando em menor teor de H2 no biogás quando presente, porém, maior conversão de sacarose e produção de H2. O pré-tratamento térmico não inibiu a metanogênese, sendo as condições operacionais mais importantes para a seleção dos microrganismos. TCS e TSS com TDH de 0,5 h apresentaram produção de H2 similar e o material suporte afetou apenas as rotas metabólicas. Entre todas as operações, TCS e UASB com TDH de 2 h alcançaram os maiores valores de rendimento de H2 (YH2), respectivamente, 1,99 ± 0,36 e 2,56 ± 0,84 molH2.mol-sac-1, através da via metabólica do etanol. TCS2 também demonstrou estabilidade e, apesar de o U2 ter gerado maiores porcentagens de H2 no biogás, pode ser apontado como o mais eficiente para a produção de H2. A relação C:N:P, Fe+2 e Ni+2 tiveram efeito significativo sobre a produção de H2, e YH2 ótimo foi estimado para concentrações de 4,53 mgFe+2.L-1 e 0,045 mgNi+2.L-1. / The thermophilic anaerobic digestion is a suitable option for wastewater discharged at high temperatures; in addition, it is suitable for more efficient pathways for H2 production. However, the results found in literature have divergences; the H2 yields are lower than the theoretical possible value and only few studies evaluated different types of reactors and defined the more advantageous one. Therefore, this study evaluated H2 production from sucrose in three types of reactor: upflow anaerobic sludge blanket (UASB), upflow tubular reactor with packed-bed (TCS) and without support materials (TSS), operated at 55°C. The hydraulic retention time (HRT) applied to UASB reactor was 12, 6 and 2h and to TCS and TSS was 2 and 0.5h.Thermal pretreatment (at 100°C, for 15 min) was applied to the methanogenic inoculum of UASB and TCS and TSS was inoculated through natural fermentation process. The effect of nutrients and the optimal concentration of t nutrients for H2 production were evaluated through batch assays. At HRT of 2h, the support material affected the mass transferring, leading to lower content of H2 in the biogas when it is used; however, in this condition it was found higher sucrose conversion and H2 production. The operational conditions showed to be more efficient for methanogenesis than pretreatment. TCS and TSS at HRT of 0.5h presented similar H2 production and the support material affected only the metabolic pathways. Among all the conditions assessed, TCS and UASB at HRT of 2h reached the highest values of H2 yield highest YH2, respectively, 1.99 ± 0.36 and 2.56 ± 0.84 molH2.mol-sac-1, through ethanol pathway. TCS2 demonstrated stability production also and, despite the U2 have achieved higher percentage of H2 in biogas, it can be pointed out as more efficient for H2 production. The ratio C:N:P, Fe+2 and Ni+2 showed significant effect on H2 production, and the optimal YH2 was estimated for 4.53 mgFe+2.L-1 e 0.045 mgNi+2.L-1.

The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

Significant advances have been made in the understanding of living/controlled radical polymerization processes since their discovery in the early 1990’s. These processes enable an unprecedented degree of control over polymer architecture that was previously not possible using conventional radical polymerization processes, and this has made possible the synthesis of many new and interesting materials. However, there has been only limited success in commercializing these new methods. Recently there has been increased focus on the development of more industrially viable processes. Dispersed aqueous phase reactions have received much attention because these water-based processes have several technical, economic, and environmental benefits over the more common solution and bulk reactions that were originally developed. Likewise, there has been some investigation of using continuous reactors that have potential technical and economic benefits over the more commonly employed batch reactors. This thesis presents an in-depth study that combines the three aforementioned technologies: living/controlled radical polymerization, dispersed phase aqueous reactions, and continuous reactors. Specifically, the system of interest is a nitroxide-mediated miniemulsion polymerization reaction in a continuous tubular reactor to produce polymer latex. Design of the continuous tubular reactor is discussed in some detail with a focus on specific technical challenges that were faced in building a functional apparatus for this system. Scoping experiments are described which identified a significant effect of temperature ramping rate that is critical to understand when moving to larger scale reactors for this system. The unexpected phenomenon of room temperature polymerization initiated by ascorbic acid is also described. There is demonstration for the first time that bulk and miniemulsion polymers can be produced in a tubular reactor under controlled nitroxide-mediated polymerization conditions, and copolymers can be produced. A detailed residence time distribution study for the tubular reactor is also shown, and several interesting phenomena are discussed that have implications on the practical operating conditions of the tubular reactor. This particular study makes it clear that one should experimentally verify the residence time distribution within a continuous system with the reactants of interest, and that model systems may not give an accurate picture of the real system. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2010-12-20 12:00:37.974

A digestão anaeróbia termofílica é uma opção vantajosa para efluentes descartados a altas temperaturas, além de estimular rotas mais eficientes de produção de H2. No entanto, os resultados da literatura divergem bastante, os rendimentos de H2 são inferiores ao valor teórico possível e poucos estudos avaliaram diferentes configurações para indicar a mais eficiente. Assim, este estudo avaliou a produção de H2 a partir da sacarose em três tipos de reator: reator anaeróbio de fluxo ascendente e manta de lodo (UASB), reator tubular de fluxo ascendente com leito empacotado (TCS) e sem material suporte (TSS), operados a 55°C. Os tempos de detenção hidráulica (TDH) aplicados ao reator UASB foram 12, 6 e 2 h e aos reatores TCS e TSS foram 2 e 0,5 h. Pré-tratamento térmico (100°C por 15 min) foi aplicado ao inóculo metanogênico do UASB e TCS e TSS foram auto inoculados. O efeito de nutrientes e a concentração nutricional ótima para a produção de H2 foram investigados através de ensaios em batelada. Com TDH de 2 h, o material suporte afetou a transferência de massa, resultando em menor teor de H2 no biogás quando presente, porém, maior conversão de sacarose e produção de H2. O pré-tratamento térmico não inibiu a metanogênese, sendo as condições operacionais mais importantes para a seleção dos microrganismos. TCS e TSS com TDH de 0,5 h apresentaram produção de H2 similar e o material suporte afetou apenas as rotas metabólicas. Entre todas as operações, TCS e UASB com TDH de 2 h alcançaram os maiores valores de rendimento de H2 (YH2), respectivamente, 1,99 ± 0,36 e 2,56 ± 0,84 molH2.mol-sac-1, através da via metabólica do etanol. TCS2 também demonstrou estabilidade e, apesar de o U2 ter gerado maiores porcentagens de H2 no biogás, pode ser apontado como o mais eficiente para a produção de H2. A relação C:N:P, Fe+2 e Ni+2 tiveram efeito significativo sobre a produção de H2, e YH2 ótimo foi estimado para concentrações de 4,53 mgFe+2.L-1 e 0,045 mgNi+2.L-1. / The thermophilic anaerobic digestion is a suitable option for wastewater discharged at high temperatures; in addition, it is suitable for more efficient pathways for H2 production. However, the results found in literature have divergences; the H2 yields are lower than the theoretical possible value and only few studies evaluated different types of reactors and defined the more advantageous one. Therefore, this study evaluated H2 production from sucrose in three types of reactor: upflow anaerobic sludge blanket (UASB), upflow tubular reactor with packed-bed (TCS) and without support materials (TSS), operated at 55°C. The hydraulic retention time (HRT) applied to UASB reactor was 12, 6 and 2h and to TCS and TSS was 2 and 0.5h.Thermal pretreatment (at 100°C, for 15 min) was applied to the methanogenic inoculum of UASB and TCS and TSS was inoculated through natural fermentation process. The effect of nutrients and the optimal concentration of t nutrients for H2 production were evaluated through batch assays. At HRT of 2h, the support material affected the mass transferring, leading to lower content of H2 in the biogas when it is used; however, in this condition it was found higher sucrose conversion and H2 production. The operational conditions showed to be more efficient for methanogenesis than pretreatment. TCS and TSS at HRT of 0.5h presented similar H2 production and the support material affected only the metabolic pathways. Among all the conditions assessed, TCS and UASB at HRT of 2h reached the highest values of H2 yield highest YH2, respectively, 1.99 ± 0.36 and 2.56 ± 0.84 molH2.mol-sac-1, through ethanol pathway. TCS2 demonstrated stability production also and, despite the U2 have achieved higher percentage of H2 in biogas, it can be pointed out as more efficient for H2 production. The ratio C:N:P, Fe+2 and Ni+2 showed significant effect on H2 production, and the optimal YH2 was estimated for 4.53 mgFe+2.L-1 e 0.045 mgNi+2.L-1.

No description available.

Orientador: Carlos Alberto Gasparetto / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-08T22:28:21Z (GMT). No. of bitstreams: 1 Ohata_SueliMarie_D.pdf: 1133009 bytes, checksum: d9e555381242748bb00e413dc46b8c7d (MD5) Previous issue date: 2007 / Resumo: Os reatores de recirculação representam uma tecnologia alternativa muito atraente para o processo de hidrogenação, tecnologia esta ainda não totalmente desenvolvida para a hidrogenação de óleos vegetais. Os reatores convencionais utilizados no processo de hidrogenação possuem agitação mecânica, sistema de injeção de hidrogênio na base, e necessitam de condições mais severas de operação, como a temperatura e a pressão. Em um reator que opera num sistema de recirculação, um ejetor tipo Venturi e utilizado, o qual proporciona uma grande transferência de massa entre as fases presentes, dispensando a agitação mecânica, alem de requerer quantidades menores de catalisador, demandar menos hidrogênio e trabalhar com pressão, temperatura e tempo de reação menor. Foram encontradas poucas informações na literatura a respeito do processo de hidrogenação de óleos vegetais através do reator de recirculação, desta forma, o objetivo deste trabalho foi analisar o processo de hidrogenação de óleo de soja em um reator de recirculação através da modelagem e simulação. Para a formulação do modelo que descreve este sistema, foram considerados os fenômenos de transferência de massa, alem da cinética da reação. A partir das equações obtidas, propos-se uma metodologia para solucionar o sistema de equações diferenciais que descrevem o sistema. Foram propostos dois modelos para o estudo: reator em batelada, resolvido analiticamente e uma associação de um reator CSTR em serie com um PFR com dispersão axial, resolvido pelo método da colocação ortogonal. Ambos os modelos descreveram adequadamente o processo de hidrogenação nas condições estudadas / Abstract: Loop reactors represent a very attractive alternative technology to the hydrogenation process, but this technology was not totally developed for the hydrogenation of vegetable oils. The conventional reactors used for the hydrogenation process have mechanical agitation, system of injection of hydrogen in the basis and they need more severe conditions of operation, as the temperature and the pressure. In a reactor that operates in a system loop, an ejector type Venturi is used, which provides an high mass transfer rate between the present phases, without mechanical agitation, needs less catalyst, demands less hydrogen and works with lower values of pressure, temperature and time of reaction. There is very little information in the literature about the hydrogenation process of vegetable oils in a loop reactor, thus, the purpose of this study was to analyse of the process of hydrogenation of soybean oil in a loop reactor by modelling and simulation. For the formulation of the model that describes this system, the phenomena of mass transfer and kinetics of the reaction were considered. From the balance equations, a method was considered to solve the system of differential equations that describe the system. Two models of reactors were proposed for the study: batch reactor, solved analytically and an association of a reactor CSTR in series with a PFR with axial dispersion, solved by orthogonal collocation method. Both models described the process of hydrogenation appropriately in the studied conditions / Doutorado / Doutor em Engenharia de Alimentos

Le glycérol est un coproduit de la filière des biocarburants obtenu par transestérification destriglycérides. Avec le développement des biocarburants, la production de glycérol est en pleine croissance.La consommation de glycérol comme additif dans les industries cosmétique, pharmaceutique et agroalimentairen’augmentant pas de manière aussi significative, l’excédent doit être valorisé. L’une des voies devalorisation est la synthèse du carbonate de glycérol qui est un intermédiaire intéressant pour la chimie fine.La méthode de synthèse utilisée au sein de l’industrie Novance est la carbonylation du glycérol par l’urée enprocédé discontinu. Cette réaction produit, en plus du carbonate de glycérol, une grande quantitéd’ammoniac gazeux extrait du milieu réactionnel par dépression. L’ampleur de ce dégagement gazeux ainsique son irrégularité au cours du temps représente la limitation de production du procédé discontinu. Le sujetde cette étude est de développer le procédé continu de cette synthèse afin de pallier ce problème. Pourréaliser le suivi de la réaction, des méthodes analytiques ont été développées dans un premier temps. Avecces outils, les connaissances du système discontinu ont été approfondies pour déterminer les critères dechoix du procédé continu. Une unité de désorption réactive a été ensuite conçue pour créer un systèmebiphasique gaz-liquide à contre-courant. Une série d’essais préliminaires a permis le développement duprocédé qui a été optimisé par un plan de Doehlert. / Glycerol is a by-product of biofuels obtained by transesterification of triglycerides. With developmentof biofuel, glycerol production is growing. The use of glycerol in cosmetic, pharmaceutical and food industriesis not increasing in the same way, so the surplus should be preferable to market. One way of development isthe synthesis of glycerol carbonate which is an interesting intermediate for fine chemistry. The synthesisused by Novance is carbonylation of glycerol by urea with a batch process. This reaction produces, as wellas glycerol carbonate, a high quantity of gaseous ammonia extracted from reactive mixture in a vacuum. Thescale of this gaseous emission and its irregularity during synthesis show the limits of production using abatch process. The aim of this study is to develop the continuous process of the synthesis to solve thisproblem. To carry out the monitoring of the reaction, at first, analytical methods were used. With suchmethods, knowledge of the batch process was improved in order to determine the best criteria for acontinuous process. A unit of reactive desorption was then elaborated to create a liquid-gas biphasic systemin a counter-flow configuration. A series of preliminary experiments were performed to develop the processwhich was optimised by a Doehlert plan.