Orientador: Flávio Vasconcelos da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T15:49:40Z (GMT). No. of bitstreams: 1 Navarro_AlexandreKhaeWu_M.pdf: 4067789 bytes, checksum: 20f4684078783b9a38711e856a726e6e (MD5) Previous issue date: 2012 / Resumo: O controle de distribuições de cristais é de grande importância para a indústria química de alta tecnologia, encontrando especial aplicação na produção de fármacos e alimentos. Nestas indústrias, outra característica é igualmente importante: polimorfismo. Legislações específicas comumente requerem a presença de um determinado tipo de polimorfo. Como o controle para obtenção destas características é de relevância industrial e tipicamente de difícil realização, neste trabalho, foi estudado o controle da cristalização do ácido L-glutâmico por resfriamento visando obter um único polimorfo e maximizar o tamanho dos cristais ao final da batelada. Este tema foi abordado utilizando controle ótimo através de três estratégias diferentes: controle ótimo em malha aberta, controle ótimo em malha aberta com rastreamento de temperatura e concentração e controle ótimo em malha fechada. As otimizações foram realizadas no software Scilab através de um método quasi-newton em esquema sequencial, de forma que os momentos da distribuição de cristais eram simulados e a curva de resfriamento ajustadas com base na simulação. Para lidar com o efeito de dissolução total de um dos polimorfos, característica que não é capturados pelos momentos populacionais, foi utilizado um loop de integração baseado na interpretação física dos valores dos momentos populacionais. Ao final do trabalho, verificou-se que a estratégia de controle ótimo em malha fechada obteve melhores resultados / Abstract: Crystal size distribution control is of great importance to high-end chemical industry, especially in applications to the production of pharmaceuticals and foods. In these industries, another crystal characteristic is equally important: polymorphism. Strict regulations often require that only an specific type of polymorph may be present in a determined product. As controlling these factors is both of industrial relevance and typically difficult, in this work, the control of batch L-glutamic acid crystallization by cooling aiming to obtain one specific polymorph while maximizing crystal size at the end of the operation. This theme was approached by using optimal control and three different strategies: open-loop optimal control, open-loop optimal control with temperature and concentration tracking, and closed-loop optimal control. The optimizations were performed in Scilab through a quasi-newton method in a sequential process so that the moments of the crystal size distribution were simulated and the cooling curves adjusted based on the simulation and the objective. To deal with the total dissolution of one of the polymorphs, a feature not captured by the populational momentts, a special integration loop was used based on the physical interpretation of the moment values. Finalluy, at the end of the study, it was found that the closed-loop optimal control approach provided better results / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Bioelectrocatalytic systems are based on biological entities, such as enzymes, whole cells, parts of cells or tissues, which catalyse electrochemical processes that involve the interaction between chemical change and electrical energy. In all cases, biocatalysis is implemented by enzymes, isolated or residing inside cells or part of cells. Electron transfer (ET) phenomena, within the protein molecules and between biological redox systems and electronics, enable the development of various bioelectrocatalytic systems, which can be used both for fundamental investigations of enzymatic biological processes by electrochemical methods and for applied purposes, such as power generation, bioremediation, chemical synthesis and biosensing. Electrical communication between the biocatalyst’s redox centre and an electrode is essential for the functioning of the system. This can be established using two main mechanisms: indirect ET and direct ET. The efficiency of the ET influences important parameters such as the turnover rate of the biocatalyst, the generated current density and partially the stability of the system, which in their turn determine response time, sensitivity, detection limit and operational stability of biosensing devices or the power densities and current output of biofuel cells, and hence should be carefully considered when designing bioelectrocatalytic systems. This thesis focuses on approaches that facilitate ET in bioelectrocatalytic systems based on indirect and direct ET mechanisms. Both fundamental aspects of ET in bioelectrocatalytic systems and applications of such systems for biosensing and power generation are considered. First, a new hydrophobic mediator for oxidases – unsubstituted phenothiazine and its improved ET properties in comparison with commonly used mediators are discussed. Application of the mediator in electrochemical biosensors is demonstrated by glucose, lactate and cholesterol sensing. Utilisation of mediated biocatalytic cholesterol oxidation, as the anodic reaction for the construction of a biofuel cell acting as a power supply and an analytical device at the same time, is investigated to deliver a selfpowered biosensor. Also the enhancement of mediated bioelectrocatalysis by employment of microelectrodes as a transducer is examined. The effect of surface roughness on the current response of the microelectrodes under conditions of convergent diffusion is considered. The applicability of the laccase-based system for total phenol analysis of weakly supported water is demonstrated. Finally, a new electrochemical approach derived from collision-based electrochemistry applicable for examination of the ET process of a single enzyme molecule is described. All together, the results presented in this thesis contribute to the solution of the ‘electronic coupling problem’, arising when interfacing biomolecules with electronics and limiting the performance of bioelectrocatalytic systems in specific applications. The developed methods to facilitate ET will hopefully promote future biosensing devices and biofuel cells. I believe the new approach for investigation of ET processes at a single enzyme molecule will complement existing single molecule techniques, giving further insights into enzymatic ET mechanisms at the molecular level and filling the gap between fundamental understanding of biocatalytic processes and their potential for bioenergy production.

Fossil based energy resources are dominating the world’s primary energy consumption for the last century. However, with decreasing crude oil reservoirs and the role they play in global warming by emitting greenhouse gases, the focus has been turned towards improved utilization of renewable resources and the need for new, sustainable fuels and chemicals is more urgent than ever. Biomass is a carbon neutral resource that can be used to produce biofuels and other useful chemicals. One such chemical is 1-butanol (or simply butanol), which has great potential as a gasoline substitute because of its favorable fuel properties. Butanol can be produced from acetone, butanol and ethanol (ABE) fermentation using e.g. Clostridium acetobutylicum. However, the concentration of butanol in fermentation in the resulting broth is limited to ca. 20 g/L due to its toxicity for microorganisms. Butyric acid is a precursor to butanol, which is produced prior to butanol in ABE fermentation. Butyric acid is an important industrial chemical, which can be further converted into a number of commercial compounds e.g. acetate butyrate, butyl acetate and butanol. Arginine is a semi-essential amino acid that has vast applications in the field of pharmaceutical and food industry. In addition, arginine can replace inorganic nitrogen as nitrogen source in fertilizers. It can be produced via fermentation of sugars using engineered microorganism like E. Coli, but like butanol its concentration is restricted to approximately 12 g/L. Due to low concentration of these useful chemicals in the resulting fermentation broths recovery of these chemicals remain challenging with today’s options and therefore  novel recovery process should be developed. In this study, zeolite adsorbents were used to recover butanol, butyric acid and arginine from model and real fermentation broths. Zeolite MFI adsorbent efficiently adsorbed butanol from model solutions with a saturation loading of 0.11 g/g- zeolite. On the other hand, adsorption of butyric acid was found to be strongly pH dependent, with high adsorption below and little adsorption above the pKa value of the acid. A structured adsorbent in the form of steel monolith coated with a silicalite-1 film was also used and performance was evaluated by performing breakthrough experiments at room temperature using model ABE fermentation broths and the results were compared with those obtained using traditional adsorbent sin the form of beads. Desorption studies showed that a high quality butanol product with purity up to 95.2% for butanol-water system and 88.5% for the ABE system can be recovered with the structured silicalite-1 adsorbent. Further, zeolite X adsorbents in the form of powder and extrudates was used to recover arginine from a real fermentation broth and also from aqueous model solutions. To the best of our knowledge, this is the first time recovery of arginine from real fermentation broths using any type of adsorbent is reported. Arginine loading of 0.15 g/g was observed at pH 11 using zeolite X powder. The selectivity for arginine over ammonia and alanine from the fermentation broth at pH 11 was 1.9 and 8.3, respectively, for powder and 1.0 and 4.1, respectively, for extrudates. Synthesis gas (CO + H2) can be produced e.g.by gasification of lignocellulose biomass. This synthesis gas can be used to produce methanol, which subsequently may be converted into gasoline using zeolite ZSM-5 catalyst. However, during Methanol to Gasoline (MTG) process, undesirable carbon residue (coke) is formed that gradually reduces the activity of catalyst. It was hypothesized that intracrystalline defects in the zeolite formed during conventional synthesis may accelerate the deactivation rate by coke formation. In this work, a novel ZSM-5 zeolite catalyst essentially free of intracrystalline defects was synthesized and evaluated in the  MTG reaction,. The novel catalyst showed significantly higher resistance towards deactivation by coke formation as compared to a reference catalyst containing defects.

A novel operational policy, the Process Intermediate Storage (PIS) operational policy, is introduced and used to synthesize, schedule and design multipurpose batch plants. The model is based on the State Sequence Network (SSN) and non-uniform discretization of the time horizon of interest model developed by Majozi&Zhu (2001). Two cases are studied to determine the effectiveness of the operational policy. A plant without dedicated intermediate storage is considered in the first case. In this case the throughput is maximized with and without the use of the PIS operational policy. The use of the PIS operational policy results in a 50% improvement in the throughout. The second case is used to determine the minimum amount of intermediate storage while maintaining the throughput achieved with infinite intermediate storage. This resulted in a 33% reduction in the amount of dedicated intermediate storage. The models developed for both cases are MILP models. A design model is then developed to exploit the attributes of the PIS operational policy. The design model is a MINLP due to the capital cost objective function. This model is applied to a literature example and an industrial case study and in both cases results in improved flowsheets and reduced capital cost. / Dissertation (MEng)--University of Pretoria, 2008. / Chemical Engineering / unrestricted

Biomass combustion is an interesting alternative to fossil fuel. Modeling and simulation is used for design optimization of biomass boilers and furnace. It is difficult to develop a sufficiently accurate and computationally efficient model because the combustion system is highly complicated multi-scale, multi-phase and multi-physics problem. The study of biomass combustion in different scales allows engineers to understand the combustion process and tochoose necessary simplification to develop a computationally efficient model.The chemical and physical properties of fuels are altered during different fuel preparation methods (i.e. pretreatment and pelletization), and as a result the fuel conversion is also affected. The aim of this thesis is to understand thermal conversion of those chemically or physically altered fuels. Both experimental and modeling techniques were chosen to addressthe aim. Experiments were performed in thermogravimetric analysers, isothermal macro thermogravimeters (iTG), and a pot furnace to account fuel conversion in micro-, meso- and macro scale. In addition, three different types of mathematical model were developed. They are (i) a simplified particle pyrolysis model, (ii) two detailed numerical models that simulate particle pyrolysis and char oxidation and (iii) finally a computational fluid dynamic (CFD) model of combustion of biomass particles in a bed. The results indicate that both the intrinsic and the apparent conversion of the fuel wasinfluenced by the process conditions of fuel preparation methods. Intrinsic pyrolysis reactivitywas reduced due to mild pretreatment; however, it was increased with further increase in pretreatment severity. In contrary, severity of pelletization tends to reduce the apparent reactivity of pellets combustion. It was also investigated that how each physical and chemical parameter should be modelledfor a untreated biomass (i.e. wood logs) and a densified biomass (i.e. pellets) through parametric studies with a detailed particle simulation. The result shows that a model for wood logs should exclude convective heat transfer by volatiles if the fibers align to longitude direction while it is important part in the models for pellets. Devolatilization of wood logs was expressed as endothermic reactions while the model results showed best agreement withexperimental data of wood pellets when the heat of reaction was assumed to be zero, possibly due to the secondary reactions. Then, it was demonstrated that a constitutive equation, i.e. analytical solution of the shrinking core model, is sufficient to express devolatilization rate of thermally-thick particles at the temperature of 1173 K. While studying apparent oxidation of wood pellet char , it was found that change in intrinsic char oxidation reactivity due to different pyrolysis conditions does not influences the model prediction at high temperature. In addition, at high temperature, the reaction front became thin and reaction rate was hardly affected by temperature.It was also found by the simulation of pellet bed combustion that the apparent density of the particle significantly affected the flame velocity. / Godkänd; 2015; 20150925 (amibis); Nedanstående person kommer att disputera för avläggande av teknologie doktorsexamen. Namn: Amit Biswas Ämne: Energiteknik/Energy Technology Avhandling: Effect of Chemical and Physical Properties on Combustion of Biomass Particle. Opponent: Professor Fabrizio Scala, Dept of Chemical, Materials and Process Engineering, University Federico II of Naples, Naples, Italy. Ordförande: Bitr professor Kentaro Umeki, Avd för energivetenskap, Institutionen för teknikvetenskap och matematik, Luleå tekniska universitet, Luleå. Tid: Torsdag 19 november, 2015 kl 10.00 Plats: E231, Luleå tekniska universitet

På SCA Östrands massafabrik i Timrå produceras två olika typer av pappersmassa,blekt sulfatmassa och kemitermomekanisk massa (CTMP). Idag produceras ungefär 430 000 ton blekt sulfatmassa och 95 000 ton CTMP per år. Just nu pågåren om- och nybyggnation av sulfatmassalinjen inom projektet Helios. Målet med projektet är att under 2018 ta i drift en fabrik med en kapacitet att producera 900 000 ton blekt sulfatmassa per år. I och med utbyggnaden har fabriken fått en ny miljödom (som ett resultat av verksamhetstillståndsansökan) med villkor attförhålla sig till. I miljödomen presenteras ett antal olika villkor; utredningsvillkor, utsläppsvillkor och riktvärden. Ett av villkoren är ett utredningsvillkor som gäller utredning av rökgasreningstekniken SNCR (selektiv icke-katalytisk reduktion) för att rena rökgaserna från fabrikens ångproducerande enheter, barkpannan (ÅP1)och sodapannan (SP6), från NOx. Syftet med examensarbetet var att i ett första steg i utredningen av utredningsvillkoret undersöka möjligheterna till att använda SNCR som rökgasrening på ÅP1 för att rena rökgaserna från NOx. För att utreda möjligheterna att använda SNCR på ÅP1 gjordes temperaturmätningar av rökgaserna i pannans övre del och en temperaturprofil över pannan bestämdes. Vidare undersöktes olika metoder av SNCR och andra sekundära rökgasreningsmetoder i en litteraturstudie och i en undersökning av marknaden som bland annat innehöll referensbesök på anläggningar med olika SNCR-system.En grov kostnadsmässig analys genomfördes också genom att beräkna teoretiskautsläppsmängder för de nya förutsättningarna efter Helios, NOx-avgiften och kemikalieförbrukningen i ett hypotetiskt fall där SNCR installeras. Under de förutsättningar som temperaturmätningarna gjordes framkom det att det inte är möjligt att använda sig av SNCR för att reducera NOx-utsläppen från ÅP1. Mätningarna visade dock att det är möjligt att använda SNCR som reningsmetod vid laster högre än 72 ton ånga/h om det finns ett linjärt samband mellan last(ton ånga/h) och rökgastemperaturen.

Detta arbete är en delstudie i projektet Seafarm. Syftet med denna studie är att utreda om algen Laminaria Digitata och vassen Phragmites Australis är lämpliga substrat i en samrötningsprocess för biogasproduktion. Metoden som användes är experimentell och utfördes under 35 dagar med en tvåstegsreaktor bestående av en lakbädd och en UASB-reaktor. Under försökets gång upptäcktes vissa fel och brister hos apparatuppställningen vilka orsakade läckage och andra brister. Detta resulterade i ett systemförslag med skiss till en ny lakbädd samt optimering av driftparametrar om försöket ska återupprepas. Efter 35 dagar avslutades försöket och utifrån den data som sammanställts uppvisar processen en bra metanpotential på 589 liter CH 4/kg COD. Processen uppvisade en låg alkalinitet med ett sjunkande pH som till följd av inmatning. Detta var grunden för den låga belastningen som processen klarade av. För framtida försök för just dessa substrat så rekommenderas en tillförsel av buffert så att alkaliniteten ökar och även möjligheterna för en högre belastning.

During the production of steel, an oxide scale is formed on the surface and to achieve anadequate quality of the surface the scale needs to be removed. Acid pickling is a surfacetreatment where the oxide scale is removed by acid. Over time the amount of dissolved metals in the acid solution increases leading to a decrease in the pickling efficiency, hence the acid solution needs to be renewed. The renewing can be performed by an operation process called acid retardation. In this process, the spent pickling solution passes through a column packed with an ion exchange material, resin. The absorption of strong acids is preferred by the resin, hence the movement of the acids in the resin bed will be retarded relative to the movement of the metal ions. Regeneration of the resin occurs when water is passing through the resin bed counter current to the flow of the spent pickling solution. This generates a by-product with low acid and high metal content, and a product containing high acid and low metal. The aim of this thesis was to investigate the acid retardation with regards to separation efficiency and the behaviour of acid and metal in the column. The results can further be used as the groundwork for a deeper understanding of the acid retardation and how to optimize the process. Experiments were performed in lab-scale columns with synthetic spent pickling solutions containing sulfuric, nitric and hydrofluoric acid and iron in different mixtures. During the experimental work, variation of the acid and metal concentration, the type of resin and the height of the column were performed. The results from the experimental work show that a concentration dependence between the concentration of acid and metal exists and the performance of different resin types varies depending on the acid and metal solution tested. The height might also affect the separation, but it is recommended that this is further investigated. Other recommendations for further work with a focus on understanding the acid retardation for optimization include variations of the volume of solution added to the column, variation in flow rate and slurry packing of the resin.

Materials that are light weight, low cost and have high hydrogen storage capacity are essential for on-board vehicular applications. Some reversible complex hydrides are alanates and amides but they have lower capacity than the DOE target (6.0 wt %) for 2010. High capacity, light weight, reversibility and fast kinetics at lower temperature are the primary desirable aspects for any type of hydrogen storage material. Borohydride complexes as hydrogen storage materials have recently attracted great interest. Understanding the above parameters for designing efficient complex borohydride materials requires modeling across different length and time scales. A direct method lattice dynamics approach using ab initio force constants is utilized to calculate the phonon dispersion curves. This allows us to establish stability of the crystal structure at finite temperatures. Density functional theory (DFT) is used to calculate electronic properties and the direct method lattice dynamics is used to calculate the finite temperature thermodynamic properties. These computational simulations are applied to understand the crystal structure, nature of bonding in the complex borohydrides and mechanistic studies on doping to improve the kinetics and reversibility, and to improve the hydrogen dynamics to lower the decomposition temperature. A combined theoretical and experimental approach can better lead us to designing a suitable complex material for hydrogen storage. To understand the structural, bulk properties and the role of dopants and their synergistic effects on the dehydrogenation and/or reversible rehydrogenation characteristics, these complex hydrides are also studied experimentally in this work.

Thermal oil oxidation is an important reason for the engine oil degradation in trucks. Having a comprehensive model that includes all the influential factors while it is feasible for being implemented in the ECUs, was aimed for this work. Therefore, the chemical investigating of the problem leaded to propose a first kinetic model and its thermal analysis caused modelling the oil thermal behaviour. The latter was developed for four compartments: Bearings, turbocharger, piston cooling and oil sump in the oil path through the lubrication system, because the highest oil temperature happens due to friction, combustion of fuels and exhaust gas transportation. Independency from the design parameters of the compartments and simplicity of models for the ECU implementation caused to investigate two various modelling hybrid approach: physical modelling and control theory approach. The first one was done for the bearings and piston cooling, and showed a high level of complexity leading to switch to the second approach. The latter was applied for all compartments while it satisfied requested requirements. To adjust and evaluate the models, an experimental campaign was devoted to acquiring the needed parameters with consideration of the project budget. Also using the previous simulation and experimental efforts at the company provided a possibility to develop flow rate sub-models used in the thermal modelling. The proposed model for all compartments, well predicted the oil thermal behaviour for both stationary and dynamic operating conditions. A comparison between the experimental data for the oil in the oil sump and turbo charger was done to show the reliability of the related models in both stationary and transient statuses. For the bearings, the simulation data for stationary condition were applied as a reference. The modelled oil temperature after piston cooling was compared to a set of experimental data that presented the probable temperature in some conditions close to stationary operating points.