Monitoring the limiting reactant concentration is a key question to maximize the productivity and to guarantee the safety of exothermic fed-batch processes. However in most applications, the concentration cannot be measured in real-time since suitable devices do not exist or are too expensive; the concentrations are then measured by off-line analyses. In this context monitoring the concentrations via software sensors, or state observer based estimators, is an attractive option. The presence of model uncertainties is a major limitation when applying state observers to real processes. More precisely, in fed-batch exothermic reactors the bad knowledge of both the reaction kinetics and the heat transfer may prevent the use of classical observers. In this study, we propose two different approaches to estimate the concentration of the limiting reactant in a class of single phase exothermic fed-batch reactors with uncertain kinetics and heat transfer. The first approach is based on a finite time converging observer that provides an estimate for the reaction rate via the reactor energy balance equation. The concentration is then computed from the reaction rate estimate via a material balance equation. The main contribution of this approach is the use of a finite time observer to limit the reconstruction error by guaranteeing a small convergence time interval for the reaction rate estimate. The second approach is based on an interval observer that provides two bounds for the concentration by considering uncertainties related to both the heat transfer and the reaction kinetics. The final estimate is then computed as the mean of the bounds. A systematic tuning procedure has been developed for each of both estimation techniques. Both estimators have then been tested and validated with real data coming from the production of different kinds of resins carried out in 10 tons reactors.

<p> Polymerization of styrene was carried out in continuous and batch reactors using azobisis obutyronitrile as initiator and benzene as solvent. Monomer conversion, molecular weight distribution (MWD) and viscosity were measured.</p> <p> Corrections to the conventional kinetic mechanism using results from the continuous reactor were determined. These corrections were applied to the batch reactor kinetic model and the conversion and MWD thus predicted were compared to experimental results. It was found that the corrections applied to the batch system were not adequate to give accurate predictions of conversion and MWD.</p> <p> A short computer study of the effect of oscillating monomer flow and temperature, as opposed to steady flow, on a transient continuous reactor was also carried out. It was found from this study that at low conversions oscillations in monomer flow will not affect the time average conversion and molecular weight. Oscillations in temperature caused an increase in time average conversion and a decrease in time average molecular weight as compared to results obtained when the reactor was operated at a steady temperature which was the average of the oscillating temperatures.</p> / Thesis / Master of Engineering (MEngr)

Yes / This work investigates how batch reactors can be optimized to increase the yield of a desired product coupling two appealing techniques for process control and optimization: the nonlinear model predictive control (NMPC) and the dynamic real-time optimization (D-RTO). The overall optimization problem is formulated and applied to calculate the optimal operating parameters of a selected case study and the numerical results are compared to the traditional control/optimization techniques. It has been demonstrated in our previous work (Pahija et al, Selecting the best control methodology to improve the efficiency of discontinuous reactors, Computer Aided Chemical Engineering, 32, 805-810, 2013) that the control strategy can significantly affect optimization results and that the appropriate selection of the control methodology is crucial to obtain the real operational optimum (with some percent of improved yield). In this context, coupling NMPC and D-RTO seems to be the ideal way to improve the process yield. The results presented in this work have been obtained by using gPROMS® and MS C++ with algorithms of BzzMath library.

The biological treatment of wastewaters from an industry was studied. Among the more important wastewater constituents of concern were high levels of suspended solids, due to graphite and nitrocellulose, the solvents, ethanol and acetone, and nitroglycerine (NG). The goal of this project was divided into four objectives. The impacts of graphite on a microbial population were evaluated. Sequencing batch reactors (SBRs) were used to monitor the effects of graphite on mixed liquor suspended solids (MLSS), removal of soluble chemical oxygen demand (sCOD), and specific oxygen uptake rates (sOUR). Graphite appeared to have no adverse effect on the microbes. The potential benefits of adding sucrose, nitrogen, and phosphorus to SBRs were evaluated. The MLSS was maintained at 1,250 mg/L, similar to the microbial population in the suspended growth system at the industry. Sucrose addition increased the sCOD removals and sOUR. No direct effect was observed with the addition of nitrogen and phosphorus. The treatability of acetone and ethanol was studied through sOUR and batch testing to determine bacterial response to solvents. Both solvents were utilized by the microbes. The concentrations tested proved to be beneficial, not inhibitory. Ethanol and a 50/50 mixture of acetone and ethanol were more viable substrates than acetone. NG treatability was examined under anoxic and aerobic conditions in SBRs and batch biological reactors. NG degradation occurred under anoxic conditions, but was more favorable in aerobic environments. NG was degraded in all SBR tests to below detection limit (0.5 mg/L); therefore, the optimal treatment could not be determined. / Master of Science

The treatability of a high strength industrial wastewater, 9,000 mg/L as chemical oxygen demand (COD), by three sequencing batch reactor (SBRs) systems operated under alternating redox environments: anaerobic/aerobic (ANA), anoxic/aerobic (ANX), and aerobic was investigated. A synthetic wastewater was modeled after a wastewater from an existing chemical processing facility. The largest component, hydroxypivaldehyde, was unavailable for the use in this research and was substituted by pivalic acid, both of which have a tertiary carbon. No significant degradation occurred in the anaerobic phase of operation; however, 55-65% of the COD was removed during anoxic operation. Simultaneous removal of pivalic acid and acetic acid was seen in both the anoxic and aerobic reaction phases. The anoxic/aerobic SBR provided the best overall treatability of the synthetic wastewater based on: effluent quality, sludge characteristics and settling properties. The results suggested that anoxic/aerobic treatment schemes are a viable treatment alternative for industrial wastewaters containing high concentrations of organic acids, including acids with tertiary carbons. The treatability of the three alternating redox environments on the Industry's wastewater was also investigated. Again, no significant degradation of the industrial wastewater occurred during the anaerobic reaction phase. During the anoxic reaction phase, 15-20% of the COD was removed from the industrial wastewater in contrast to the high removals seen with the synthetic wastewater. The aerobic SBR provided the best COD removal for the industrial wastewater. The performance differences between the synthetic and industrial wastewaters stress the importance of treatability studies on the actual industrial wastewater. Biological treatment of the synthetic and Industry wastewaters was unable to achieve the effluent goal of 100 mg/L as COD. Sand filtration followed by granular activated carbon adsorption treatment of the effluent from the synthetic wastewater-fed ANA SBR provided the COD removal necessary to achieve the effluent goal. / Master of Science

No / This work investigates in detail several methodologies to improve the optimal control of discontinuous processes. It shows that whenever a batch dynamic optimization is solved, the optimum is related to the control methodology adopted and the result is a sub-optimum since other more (or apparently less!) appealing control methodologies might lead to "better" optimal solutions. The selection of the best control methodology for the dynamic optimization is broached for batch reactors using gPROMS models builder 3.5.2 for dynamic modeling and BzzMath 6.0 optimizers to handle control and optimization issues.

A remoção de compostos sulfurosos (sulfeto/sulfato) de águas residuárias tem grande importância para a saúde humana e para o ambiente. A biorremediação desses compostos, através da utilização de bactérias fototróficas anoxigênicas apresenta-se como alternativa viável ecológica e economicamente. Neste projeto de pesquisa realizaram-se ensaios em reatores em batelada expostos à iluminação fluorescente, com a finalidade de avaliar a utilização de sulfeto por cultura enriquecida de sulfubactérias fototróficas verdes, proveniente de sedimento de lagoa de estabilização. A avaliação da utilização de sulfeto e os resultados da cinética de crescimento da cultura visam a possibilidade de aplicação das bactérias fototróficas anoxigênicas no tratamento de águas residuárias. Na avaliação cinética de crescimento da cultura enriquecida de sulfubactérias fototróficas verdes foi verificado diminuição na velocidade de crescimento de 0,0346 h-1 para 0,0035 h-1 com o aumento da concentração inicial de sulfeto de 11,4 para 529,6 mg-S/L, respectivamente. O tempo de geração apresentou comportamento crescente com valores iguais a 19,98 h e 119,18 h, respectivamente. Os valores do coeficiente de conversão de sulfeto relativo ao crescimento de microrganismos (Yx/s), apresentaram diminuição progressiva com o aumento da concentração inicial de sulfeto, sendo esta queda mais acentuada no intervalo de concentrações de 40,5 a 147,2 mg-S/L. / The removal of sulphur compounds (sulfide/sulfate) from wastewaters is very important for human and for the environmental. The bioremediation of these compounds, applying anoxigenic phototrophic bacteria has been presented as a possible alternative. The aim of this work is to evaluate the utilization of sulfide by the enrichment of green sulphur bacteria proceeding from stabilization pond sediment, through the realization of batch reactors assays, which are exposed to fluorescent ilumination. The determination of the sulfide utilization and the results of the kinetic growth were done to clarify the possibility of the application of anoxigenic phototrophic bacteria in the wasterwater systems. In kinetic experiments it was observed that the specific rate of bacterial growth changed from 0.0346 h-1 to 0.0035 h-1. Then the initial sulfide concentration was increased form 11.4 mg-S/L to 529.6 mg-L. The doubling time showed an increase from 19.98 h to 119.18 h. The sulfide conversion to microorganism biomass (Yx/s) progressively decrease with the increase of sulfide concentration. Such a decrease was higher in between sulfide concentrations of 40.5 mg-S/L to 147.2 mg-S/L.

O processamento anaeróbio da vinhaça se apresenta como uma alternativa para a recuperação de energia (biogás), e reaproveitamento das suas características nutricionais através da disposição no solo. Com o intuito de elevar a eficiência energética, o presente trabalho teve como objetivo estimular a produção de metano em reatores anaeróbios em batelada de lodo granular adaptado, alimentados com vinhaça de usina sucroalcooleira, por meio da adição de metais traço. Foram avaliadas as suplementações da vinhaça com Co, Zn, Mo, Ni, Mn e W. Na Fase 1 foram realizados 4 ensaios, os reatores foram analisados individualmente nas concentrações 200 &#956;g.L-1, 350 &#956;g.L-1, 500 &#956;g.L-1 e 800 &#956;g.L-1. Na Fase 2 verificou-se o comportamento dos metais em conjunto, à concentração de 350 &#956;g.L-1 de cada micronutriente (Co, Ni, Zn, Mo, Cu e Mn). Os dados de produção acumulada de CH4 foram ajustados pelo modelo modificado de Gompertz, e foram obtidas as constantes cinéticas. Na Fase 1, verificou-se que a concentração de 200 &#956;g.L-1 de Co foi a mais adequada aos experimentos e apresentou a maior velocidade máxima de produção de CH4, 121,30 mL.d-1 (aumento de 17% na taxa de produção de metano). Nesta mesma Fase, o W apresentou indícios de inibição à concentração de 800 &#956;g.L-1, e os demais metais exibiram os melhores resultados nesta mesma concentração, a velocidade de produção (Rm) aumentou para o Mn (26%), Ni (25%), Cu (21%) e Mo (19%), e os rendimentos mais expressivos foram para Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) e Ni (0,232 mL CH4.mg-1 DQOrem). A Fase 2 não apresentou resultados satisfatórios, as verificações não indicaram variação relevante entre os reatores do ensaio e controle. / Anaerobic processing of vinasse is presented as an alternative to energy recovery (biogas), and reuse of its nutritional characteristics through the provision on the ground. In order to increase energy efficiency, this study aimed to stimulate methane production in adapted anaerobic batch reactors with granular sludge fed with vinasse from sugarcane biorefineries, through the addition of trace metals. The supplementation vinasse were evaluated with Co, Zn, Mo, Ni, Mn and W. In phase 1 four essays were realized, and micronutrient were analyzed individually in concentrations of 200 &#956;g.L-1, 350 &#956;g.L-1, 500 &#956;g.L-1 and 800 &#956;.L-1. In phase 2 it was observed the behavior of metal together, with micronutrients concentration of 350 &#956;g.L-1 (Co, Ni, Zn, Mo, Cu e Mn). The data of methanes production were adjusted by Gompertz modified model and kinetics constants were obtained. In phase 1 it was verified that the concentration of 200 &#956;g.L-1 of Co was optimal for the experiments and showed the highest maximum production velocity of CH4, 121,30 mL.d-1 (increase of 17%). In this phase W showed evidence of inhibition at a concentration of 800 &#956;g.L-1, and other metals showed the best results in the same concentration. The velocity of production (Rm) increased to Mn (26%), Ni (25%), Cu (21%) e Mo (19%), and the most significant yields were to Mo (0,267 mL CH4.mg-1 DQOrem), Zn (0,240 mL CH4.mg-1 DQOrem) and Ni (0,232 mL CH4.mg-1 DQOrem). Phase 2 did not show satisfactory results.

Este trabalho teve como objetivo avaliar o comportamento de arquéias metanogênicas e bactérias redutoras de sulfato na presença de oxigênio, em reatores anaeróbios em batelada, sob condições sulfetogênicas e mesofílicas. Os reatores foram inoculados com lodo anaeróbio proveniente de reator UASB utilizado no tratamento de água residuária de avicultura. Triplicatas de reatores foram alimentadas com meio basal ZINDER, acrescido de acetato de sódio, etanol ou lactato de sódio e sulfato de sódio, de modo a se obter relações DQO/sulfato iniciais de 1,1-1,5. O headspace dos reatores foi preenchido com \'N IND.2\' (100%) acrescido de oxigênio puro comercial (3-3,5 mg/L de oxigênio dissolvido). Os reatores anaeróbios controle foram alimentados com os mesmos substratos orgânicos, entretanto, seu headspace foi preenchido com \'N IND.2\'/\'CO IND.2\' (70/30%). Nos reatores com acetato de sódio, etanol e lactato de sódio as velocidades de produção de metano foram de 0,30 mmol/L.h, 0,41 mmol/L.h e 0,16 mmol/L.h, respectivamente, para os reatores controle. Em relação aos reatores com oxigênio os valores foram de 0,27 mmol/L.h, 0,40 mmol/L.h e 0,08 mmol/L.h, respectivamente. Na presença de acetato, etanol e lactato a redução de sulfato foi de 57% e 97%; 59,6% e 76,6%; 77,5% e 41,9%, respectivamente, nos reatores controle e com oxigênio. Nos reatores com acetato e etanol houve predomínio de organismos do domínio Archaea nos reatores controle (59,2% e 58,8%) e com oxigênio (60,7% e 54,5%), respectivamente. No reator controle contendo lactato, também ocorreu o predomínio de arquéias metanogênicas (56,2%), enquanto na presença de oxigênio houve predomínio de organismos do domínio Bacteria (63,9%). As proporções de BRS nos reatores controle e com oxigênio contendo acetato, etanol e lactato foram de 22% e 17,3%; 28% e 16,9%; 19,5% e 21,9%, respectivamente. O oxigênio não inibiu a metanogênese e nem a redução de sulfato nos reatores contendo acetato e etanol. / This work aimed to evaluate the behavior of methanogenic archaea and sulfate reducing bacteria in the presence of oxygen, using anaerobic batch reactors under sulfidogenic and mesophilic conditions. The reactors were inoculated with anaerobic sludge from UASB reactor treating poultry wastes. Third copies of the reactors were fed with ZINDER medium, increased with sodium acetate, ethanol or sodium lactate and sodium sulfate, in order to get COD/sulfate ratio of 1,1-1,5. The headspace of the reactors was filled with \'N IND.2\' (100%) and increased with oxygen (OD concentration of 3-3.5 mg/L). The anaerobic control reactors were fed with the same organics substrates, however, the headspace was filled with \'N IND.2\'/\'CO IND.2\' (70/30%). The rates of methane production were 0.30 mmol/L.h, 0.41 mmol/L.h and 0.16 mmol/L.h, in acetate, ethanol and lactate controls reactors, respectively. In oxygen reactors, the rates of methane production were 0.27 mmol/L.h, 0.40 mmol/L.h and 0.08 mmol/L.h in acetate, ethanol and lactate reactors, respectively. The rates of sulfate reduction in acetate, ethanol and lactate reactors were 57% and 97%; 59.6% and 76.6%; 77.5% and 41.9%, respectively, in control reactors and oxygen reactors. In acetate and ethanol reactors, were verified predominance of Archaea domain in control reactors (59.2% and 58.8%) and oxygen reactors (60.7% and 54.5%), respectively. In lactate control reactor also was verified predominance of Archaea domain (56.2%), whereas in lactate oxygen reactors there was predominance of cells belonging to Bacteria domain (63.9%). BRS ratio in acetate, ethanol and lactate control reactors and oxygen reactors corresponded to 22% and 17.3%; 28% and 16.9%; 19.5% and 21.9%, respectively. The addition of oxygen didn\'t inhibit the methanogenesis and sulfate reduction in acetate reactors and in ethanol reactors.

Submitted by Jean Medeiros (jeanletras@uepb.edu.br) on 2016-08-10T12:13:20Z No. of bitstreams: 1 PDF - Larissa Barreto Barbosa.pdf: 1228913 bytes, checksum: 2ac5600e4706fd0ad2c049bb9b5dba33 (MD5) / Made available in DSpace on 2016-08-10T12:13:20Z (GMT). No. of bitstreams: 1 PDF - Larissa Barreto Barbosa.pdf: 1228913 bytes, checksum: 2ac5600e4706fd0ad2c049bb9b5dba33 (MD5) Previous issue date: 2016-04-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this study, we investigated the influence of the concentration of total solids and temperature in the process of anaerobic co-digestion of organic solid waste in one batch -1 -1 reactors, using three different concentrations of total solids: 30.5 g.L (ST1); 39.5 g.L -1 (ST2) and 48.2 g.L (ST3), and three levels of temperature: ambient (average 24 ° C) (T1), 35 ° C (T2) and 40C (T3). The experimental system was built, installed and monitored for 180 days in the physical facilities of the Experimental Biological of Sewage Treatment Station (EXTRABES) of the State University of Paraíba, Campina Grande - PB, Brazil. For power reactors was prepared substrate in a proportion of 80% of crushed vegetable solid waste and sieved at 2 mm mesh and 20% anaerobic sludge from UASB reactor treating domestic sewage. The best results with regard to removal of DQOT, TKN, proteins, carbohydrates, besides solubilization of COD and increase the concentration of N-NH4, were coming from the treatment at 35 ° C. On the other hand, the total solids -1 concentration of 30.6 g.L , provided the best efficiency in the bioconversion of organic matter. The highest yield of biogas and CH4 gas was observed for treating the substrate with a lower concentration of total solids and 35 ° C. / Neste trabalho foi investigada a influência da concentração de sólidos totais e da temperatura no processo de co-digestão anaeróbia de resíduos sólidos orgânicos em reatores de batelada única, aplicando três diferentes concentrações de sólidos totais: 30,5 -1 -1 -1 g.L (ST1) ; 39,5 g.L (ST2) e 48,2 g.L (ST3), e três níveis de temperaturas: ambiente (média 24ºC) (T1), 35ºC (T2) e 40ºC (T3). O sistema experimental foi construído, instalado e monitorado por 180 dias nas dependências físicas da Estação Experimental de Tratamentos Biológicos de Esgotos Sanitários (EXTRABES) da Universidade Estadual da Paraíba, Campina Grande – PB, Brasil. Para a alimentação dos reatores foi preparado o substrato numa proporção de 80% de resíduos sólidos vegetais triturados e peneirados em malha de 2 mm e 20% de lodo anaeróbio proveniente de reator UASB tratando esgoto sanitário. Os melhores resultados em relação às remoções de DQOT, NTK, proteínas, carboidratos, além da solubilização de DQO e aumento na concentração de N-NH4, foram advindo do tratamento à temperatura de 35°C. Por outro lado, a concentração de sólidos -1 totais de 30,6 g.L , propiciou a melhor eficiência na bioconversão da matéria orgânica. A maior produção de biogás e de gás CH4 observada foi para o tratamento do substrato com menor concentração de sólidos totais e temperatura de 35°C.