Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-09-16T14:17:18Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Andréa Leão_Ver_Final.pdf: 2849890 bytes, checksum: cd4d0770cfce99861e2cf216c67ed0fb (MD5) / Made available in DSpace on 2016-09-16T14:17:18Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação_Andréa Leão_Ver_Final.pdf: 2849890 bytes, checksum: cd4d0770cfce99861e2cf216c67ed0fb (MD5) Previous issue date: 2016-02-23 / ANP / O presente estudo propõe a separação entre os triacilgliceróis (TAGs), principais constituintes dos óleos vegetais, e ácidos graxos livres (AGLs) através do processo de destilação a vácuo. A possibilidade dessa separação consiste na considerável diferença de volatilidade entre os AGLs e os TAGs. Foram preparadas misturas modelo aos óleos residuais, ou seja, combinações em diferentes proporções em massa de óleo de soja refinado (OS) e o reagente ácido oleico p.a (AO). As misturas foram destiladas nas pressões reduzidas de 0,13; 0,40; 0,67 e 1,33 kPa, sendo o processo realizado em batelada em um único estágio, sem refluxo. As amostras foram caracterizadas antes e após o processo de destilação a vácuo quanto: à massa específica, ao teor de água, ao teor de AGL (%) e à composição de ácidos graxos por cromatografia gasosa. Posteriormente, foram definidos os componentes modelo de TAG e AO e a estimativa dos parâmetros termofísicos das misturas para a simulação do processo de destilação a vácuo no software Aspen Plus V8.8, utilizando tanques flash não adiabáticos em série. O modelo termodinâmico usado foi o Non-Random Two-Liquid (NRTL). As curvas de destilação experimentais da mistura de 89,45% de OS e 10,55% de AO em massa foram melhor representadas pelas curvas de destilação simuladas, apresentando o percentual de desvios médios quadráticos de 2,5; 2,2; 2,4 e 2,5% para operações realizadas em pressões reduzidas de 0,13; 0,40; 0,67 e 1,33 kPa, respectivamente. Os dados de massa específica a 20°C dos produtos das destilações, resíduos e destilados, foram semelhantes aos do OS e AO, respectivamente. Os teores de água dos destilados (0,024% a 0,059%) e dos resíduos (0,001% a 0,014%) estão em níveis adequados para o emprego das reações de esterificação e transesterificação para a produção de biodiesel. Os teores de ácidos graxos livres dos resíduos obtidos após as destilações ficaram dentro da faixa de 0,4% a 1,2%, indicando processo de separação por destilação a vácuo efetivo. / This study proposes the separation of triacylglycerols (TAG), main constituent of vegetable oils, and free fatty acids (FFA) through the vacuum distillation process. The possibility of this separation is the considerable difference in volatility between the FFA and the TAG. Mixtures were prepared with model waste oil, or combinations of different mass ratios of refined soybean oil (SO) and the reagent oleic acid (OA). The mixtures were distilled at reduced pressures of 0.13; 0.40; 0.67 and 1.33 kPa, the process being carried out in batches in a single stage, without reflux. The samples were characterized before and after the vacuum distillation process as: the specific gravity, the water content, the FFA content (%) and the fatty acid composition by gas chromatography. Subsequently, the components were defined template TAG and OA and the estimation of parameters of mixtures thermophysical to simulate the vacuum distillation process in Aspen Plus v8.8 software using non-adiabatic flash tanks in series. The thermodynamic model used was the Non-Random Two-Liquid (NRTL). Experimental distillation curves of mixing 89.45% of SO and 10.55% of mass OA were best represented by simulated distillation curves, showing the percentage of mean deviation squared of 2.5; 2.2; 2.4 and 2.5% for operations in reduced pressures of 0.13; 0.40; 0.67 and 1.33 kPa, respectively. The specific mass of data at 20°C the distillation of the products, residues and distillates were similar to SO and OA, respectively. The content of distilled water (0.024% to 0.059%) and waste (0.001% to 0.014%) were at adequate levels for the use of esterification and transesterification reactions for biodiesel production. The contents of free fatty acids from residues obtained after distillations were within the range of 0.4% to 1.2%, indicating a separation process by distillation under vacuum effective.

La distillation réactive est l’un des procédés chimiques intensifiés les plus reconnus, qui intègre la séparation et la réaction au sein d’un même appareil. Les principaux avantages de la distillation réactive concerne l’amélioration de la conversion de la réaction, la diminution significative des investissements, des coûts de fonctionnement, de la consommation énergétique, et de la production de sous produits. Une méthodologie de conception systématique, générale et hiérarchisée de la distillation réactive discontinue avec des réactions consécutives est présentée dans ce manuscrit. La méthode élaborée est présentée sur la transestérification du carbonate de diméthyle par le procédé de distillation réactive discontinue dans une colonne avec un bac intermédiaire. Après l’acquisition de données phisicochimiques de base nécessaire à notre méthode, une nouvelle méthode de l’analyse de faisabilité pour les systèmes multiréactifs et multiconstituant a été développée. L’étape suivante est l’analyse de sensibilité afin d’explorer les effets des paramètres du procédé. Une configuration faisable, qui est entièrement réactive avec une alimentation dans la partie supérieure et inférieure de la colonne et avec un bac intermédiaire a été choisie et étudiée au cours de l’analyse de sensibilité par des simulations rigoureuses effectuées en utilisant le logiciel ProSIM Batch. / Reactive distillation, a process integrating separation and reaction in a single unit, is one of the best known intensified chemical processes. Major advantages of reactive distillation include higher conversion, reduced investment, operating costs, energy consumption, and quantity of secondary products. A systematic and hierarchic general methodology for conceptual design of multireactive batch reactive distillation (BRD) is presented in this manuscript. The elaborated method is presented on the transesterification of dimethyl carbonate by the process of batch reactive distillation in a middle vessel column.After collecting the physico-chemical basic data necessary for our method, the new method of feasibility analysis for multicomponent and multireactive systems has been developed. The next step is the sensibility analysis, when the effects of the process parameters are analysed. As a configuration feasible a fully reactive configuration of middle vessel column with entrainer feeding to the upper and lower column sections is studied by simulations using ProSIM Batch.

Poly(vinylidene) fluoride (PVDF) nano-composite membranes were prepared. The dope solution contained varied concentrations of superhydrophobic SiO2 nano-particles. The fabricated flat sheet membranes were characterized extensively by SEM, FTIR, water contact angle, LEPw, surface roughness, pore size diameter and pore size distribution. The effect of the nano-particles on the membrane performance was then analysed. The nano-composite membranes showed increased surface pore diameter, elevated water contact angle measurements with lower LEPw when compared to the neat membrane. The 7 wt. % nano-composite membrane showed the greatest flux in a VMD process with 2.9 kg/m2.h flux achieved accounting to a 4 fold increase when compared to the neat membrane. Desalination test were carried out using a 35 g/L synthetic salt water and rejection >99.98% was obtained. The best performing nano-composite dope solution (7 wt. %) was then further treated for performance enhancement by increasing the water content to increase pore size and pore size distribution followed by coating with nano-fibres. The uncoated and coated flat sheets, were characterized by SEM, surface roughness, LEPw and CAw. Flux analysis showed that the increase in water content had little effects on the VMD flux. It also suggests that; the nano-fibre layer posed very little resistance to mass transfer. A comparison of VMD and DCMD was also done experimentally.

The target of diploma thesis was to improve author’s theoretical and practical design knowledge of process engineering. In the diploma thesis a Simplified Basic Engineering Project of distillation unit has been developed. It was necessary to become familiar with the process technology and formal requirements of Basic Engineering Project. The most important parts of Basic Engineering Project are material and heat balances. Material and heat balances are the corner stones of distillation unit equipment design. Parameters of process equipment are presented in the form of equipment datasheets. The specification of pipelines is based on material and heat balances too. Inevitable part of Basic Engineering are Process Flow Diagram and Piping and Instrumentation Diagram (PFD & PID). Process Flow Diagram and Piping and Instrumentation Diagram include all equipment, piping and basic control loops.

This thesis is focused on experimental work in the domain of vacuum evaporation efficiency improvement. The first part introduces theory of liquids evaporation and its influencing factors, then multi-stage flash distillation technology. The next part of theory is an overview of other technologies used for desalination of sea water and introduction to the design of experiments. In the practical part are selected factors affecting efficiency of device and experiment plan is designed for them. When the experiment is done, optimal operating conditions of technology are designed on basis of analysis.

Desalination is one of the proposed methods to meet the ever increasing water demands. It can be subdivided into two broad categories, thermal based desalination and electricity based desalination. Multi-effect Distillation (MED), Multi-Stage Flashing (MSF), Membrane Distillation (MD) fall under former and Reverse Osmosis (RO), Electro-Dialysis (ED) fall under later. MD offers an attractive solution for seawater as well as brackish water distillation. It shows highly pure yields, theoretically 100% pure. The overall construction of a MD unit is way simpler than any other desalination systems. MD is a thermally driven diffusion process where desalination takes places in the form of water vapor transport across the membrane. It has low second law efficiency due to parasitic heat losses. The objective of the first part of the investigation is to thoroughly analyze a Direct Contact Membrane Distillation (DCMD) system from the view point of yield and exergy. The insights from exergy analysis are used in a design study, which is used for performance optimization. The first part concludes with a design procedure and design windows for large scale DCMD construction. In the second part of the investigation, focus is moved to waveguide solar energy collector. The idea behind an ideal waveguide is to reduce the complexity of modeling solar energy collection. The mathematical model provided in this analysis can be extended to a family of non-imaging optics in solar energy and serves as a benchmarking analysis tool. A waveguide is suitable for low temperature operations due to limitations on maximum continuous temperature of operation. Thus, it becomes an ideal solution for DCMD applications. A levelized cost analysis is presented for a waveguide powered DCMD plant of a 30,000 capacity. A combination of waveguide and DCMD shows levelized cost of water at $1.80/m³, which is found to be lower than previously reported solar desalination water costs. / Master of Science

Thesis (MScEng)-- Stellenbosch University, 2013. / ENGLISH ABSTRACT: The objective of this research was to obtain clean drinkable water from treated sewage effluent by using a solar-powered distillation cycle. Technologies and concepts were borrowed from the solar desalination industry to propose a unique circular distillation cell design. From the design, a specific mathematical correlation was developed to predict the distillate mass flow rate by using only evaporation and condensation temperature as inputs. This model was incorporated into a simulation model built using Transient System Simulation software. Long-term simulations were carried out to determine the operating capabilities of the design. A prototype was successfully constructed and operated. Experimental results indicated good agreement with the mass flow rate mathematical correlation. Water quality levels were tested against the South African National Standard 241 national drinking water quality standard. Four quality parameters are outside acceptable levels. Evidence suggested that acceptable quality levels could be reached. The circular distillation cell design is a major contribution made by this research. Another contribution is the simulation model capable of predicting an output for different locations. Finally, the proposed prototype is potentially a very valuable device contributing towards the reduction of consumer demand in terms of water and energy as well as the household load on the wastewater treatment system. / AFRIKAANSE OPSOMMING: Die doel van hierdie tesis is om te beskryf hoe behandelde rioolwater deur middel van ’n son aangedrewe distillasiesisteem gesuiwer kan word om drinkbare water as eindproduk te lewer. Die nodige tegnologieë en konsepte is oorgeneem uit kommersiële sonaangedrewe ontsoutingsisteme om met ’n unieke ontwerp voorendag te kom wat uit ’n sirkelvormige natuurlike konveksie distillasiesel bestaan. Met behulp van hierdie ontwerp is ’n wiskundige korrelasie ontwikkel om die gesuiwerde water se massavloei te bepaal. Slegs die verdampings- en kondensasietemperature word as insetwaardes gebruik om die massavloei te bereken. ’n Simulasiemodel is met behulp van die Transient System Simulation programmatuur gebou. Die wiskundige korrelasie is by die simulasiemodel geïnkorporeer om langtermynsimulasies te kan uitvoer. Voorts is ’n demonstrasiemodel suksesvol gebou en aangedryf. Eksperimentele resultate toon goeie ooreenstemming met die simulasieresultate. Die gesuiwerde water se gehalte is met die nationale SANS 241 drinkwaterstandaard as maatstaf getoets. Slegs vier gehalteparameters val buite die aanvaarbare vlakke, hoewel dit blyk dat hierdie elemente wel tot aanvaarbare vlakke verlaag kan word. Hierdie navorsing se grootstet bydrae is die ontwerp van die unieke sirkelvormige distillasiesel. ’n Bykomende bydra is die aanpasbaarheid van die simulasiemodel sodat dit produksievermoë op verskillende plekke kan voorspel. Die demonstrasiemodel is ’n potensieel waardevolle ontwerp wat kan bydra tot die verlaging in verbruikersaanvraag na water en energie. ’n Ontwerp van hierdie aard kan die las wat huishoudings op suiweringaanlegte vir rioolwater plaas, verlig.

Ces travaux de thèse abordent la problématique du développement d'internes destinés à la distillation réactive. La méthodologie à suivre est appliquée dans le cas des mousses céramiques en Carbure de Silicium. Le comportement hydrodynamique a été étudié ainsi que la capacité en transfert de matière validant la possible application des mousses en tant que garnissage destiné à la distillation. L'activation catalytique du support a ensuite été développée afin de dégager la méthode la plus intéressante permettant d'approcher le garnissage de référence, le KATAPAK, en termes d'activité catalytique. Le greffage d'Amberlyst 15 est alors apparu comme la voie la plus intéressante pour la possible application des mousses greffées comme interne catalytique destiné à la distillation réactive. / This work of thesis approaches the problems of the development of packings intended for reactive distillation. Methodology to be followed is so applied in the case of ceramic foam in Silicon Carbide. The hydrodynamic behaviour was studied as well as the mass transfer efficiency demonstrating the possible application of ceramic foam as a packing for distillation. The aspect of the catalytic activation of the support was then developed in order to determine the most efficiency method in terms of catalytic activity making it possible to approach reference packing, the KATAPAK. The coating of Amberlyst 15 then appeared as the most interesting way for the possible application of coating foam as catalytic packing for reactive distillation.

L'objectif de cette étude consiste à développer une approche permettant d'économiser de l'énergie de haut niveau thermique dans le procédé de la distillation atmosphérique du pétrole. Cette approche repose sur le fait que l'installation de plusieurs flashs sur le train de préchauffage de ce procédé associée à un choix approprié du plateau d'alimentation des vapeurs résultantes à la colonne de distillation, provoque une diminution de la chaleur apportée à ce train de préchauffage. Le déficit de chaleur de haut niveau thermique ainsi créé est causé par la réduction des débits des reflux latéraux de la colonne de distillation et il est compensé par de la chaleur de bas niveau thermique apportée par les effluents résiduaires disponibles dans toute la raffinerie. Cette approche peut être appliquée aux nouveaux procédés comme à l'expansion des procédés existants et l'économie d'énergie de haut niveau thermique dans le four peut atteindre les 21%. Une réduction équivalente des gaz à effet de serre est aussi observée / The objective of this thesis is to demonstrate, on thermodynamic grounds, that introducing a flash in the preheating train of an atmospheric oil distillation process , together with an appropriate feeding of the resulting vapors into the column, could potentially bring substantial energy savings by reducing the duty of the preheating furnace and by reducing the distillation column irreversibilities. This idea has been expended by showing how this can be done while keeping the throughput and the product characteristics unchanged. The outcome is that placing several flashes after the heat exchangers and feeding the corresponding vapor streams to the appropriate trays of the column, reduces the pumparound flows and then the heat brought to the preheating train. The resulting heat deficit may then be compensated in additional heat exchangers by using low level heat recuperated from the products of the distillation and/or imported from other processes. The use of this residual heat reduces the furnace duty by approximately an equivalent amount and could be as high as 21%. The approach can be applied in the design of news processes or in the revamping of existing ones

Une colonne de séparation d'air réalise un écoulement liquide-gaz à contre courant dans une structure complexe, le garnissage. Au sein de ce garnissage, l'écoulement du liquide est du type film drainé par gravité, alors que l'écoulement du gaz est turbulent. La fonction de ces contacteurs est de développer une surface d'échange interfaciale aussi grande que possible pour favoriser le transfert d'un composé chimique de la phase liquide vers la phase vapeur (et inversement) tout en offrant des pertes de charge raisonnables. Ces dispositifs sont constitués par l'assemblage de plaques métalliques ondulées, avec ou sans perforations, où deux plaques adjacentes sont respectivement inclinées d'un angle et son opposé par rapport à l'axe de la colonne. Ce type de contacteur peut être considéré comme un milieu poreux bi-structuré avec un taux de porosité élevé. Les écoulements peuvent être décrits à deux échelles : une échelle du pore et une échelle macroscopique. A cause de cette double structuration, la modélisation macroscopique des écoulements dans ce type de structure reste un problème difficile. En particulier, les mécanismes macroscopiques qui entraînent l'étalement d'un jet dans les garnissages sont incompris. Par ailleurs, une difficulté de modélisation supplémentaire est due aux effets liés à la turbulence. Au cours de cette thèse, nous avons développé, à partir d'une méthode de changement d'échelle, un modèle complet pour simuler les écoulements et le transfert de matière dans les colonnes équipées de garnissages structurés. Notre étude se focalise sur les trois points suivants. Premièrement, nous avons obtenu, à l'aide d'une prise de moyenne volumique, une loi de Darcy-Forchheimer qui inclue les effets de la turbulence. Ensuite, pour modéliser la dispersion radiale du liquide dans la colonne, nous avons trouvé pratique de séparer la phase liquide en deux films distincts, qui s'écoulent sur chaque plaque ondulée selon des directions préférentielles différentes. Ces phases fictives ne sont pas indépendantes puisque de la matière peut passer de l'une à l'autre au niveau des points de contact entre les feuilles ondulées. Finalement, nous avons proposé un modèle macroscopique pour simuler le transport d'espèces chimiques dans un système diphasique, multiconstituants. Tous les paramètres effectifs qui apparaissent dans ce modèle sont évalués à partir de solutions analytiques ou numériques de l'écoulement à la petite échelle. Les résultats de simulation ont été comparés avec succès à des mesures expérimentales obtenues en laboratoire ou sur pilote industriel. / Structured packings play a large role in chemical engineering processes involving gasliquid separation such as air distillation unit or CO2 absorption columns. Such structures maximize the exchange surface between gas and liquid while pressure drops remain low enough. Generally, the columns are operated in the counter-current flow mode : a liquid gravity film is sheared by the turbulent flow of a gas phase. The packings are made of an assembly of corrugated sheets where two adjacent sheets are respectively inclined by an angle and the opposite of this angle from the vertical axis. We can apprehend such a device as a bi-structured porous medium with high porosity defining two scales of description : a pore-scale and a macro-scale assimilated to the packing scale. Due to this peculiar structured geometry, the flow modeling from a macroscopic point of view, remains a challenging problem that has to be overcome to design enhanced devices. In particular, the macroscopic phenomena that leads to the spreading of a liquid point source at the top of a packing are still unknown, and the classical two-phase flow models in porous media failed to properly catch the liquid distribution within the column. Moreover, turbulence effects lead to additional difficulties. We developed a comprehensive mathematical model based on a multi-scale analysis to simulate gas-liquid flow through the distillation columns. We investigate three main points. First, we derived a Darcy-Forchheimer law that includes turbulence effects using the method of volume averaging. Then, to model the liquid spreading, we found convenient to split the liquid phase into two fictitious phases flowing along each sheet with a preferential direction. Moreover, these phases are not (except perhaps at very low saturation) completely independent since adjacent sheets are in contact and the liquid can flow from one sheet to the other. Finally, we proposed a macro-scale dispersion model to simulate two-phase, multicomponent transport in structured packing. All the effective properties that appear in this model are evaluated from either simulations or analytical solutions of the flow at the pore-scale. Simulation results have been successfully compared to laboratory-scale experiments and industrial-scale measurements.