Dissertations / Theses on the topic 'Aspen Plus Simulation'

The global fossil reserves are dwindling and there is need to find alternative sources of energy. With global warming in mind, some of the most commonly considered suitable alternatives include solar, wind, nuclear, geothermal and hydro energy. A common challenge with use of most alternative energy sources is ensuring continuity of supply, which necessitates the use of energy storage. Hydrogen has properties that make it attractive as an energy carrier. To efficiently store energy from alternative sources in hydrogen, several methods of hydrogen production are under study. Several literature sources show thermochemical cycles as having high potential but requiring further development. Using literature sources, an initial screening of thermochemical cycles was done to select a candidate thermochemical cycle. The copper–chlorine thermochemical cycle was selected due to its relatively low peak operating temperature, which makes it flexible enough to be connected to different energy sources. Once the copper–chlorine cycle was identified, the three main copper–chlorine cycles were simulated in Aspen Plus to examine which is the best configuration. Using experimental data from literature and calculating optimal conditions, flowsheets were developed and simulated in Aspen Plus. The simulation results were then used to determine the configuration with the most favourable energy requirements, cycle efficiency, capital requirements and product cost. Simulation results show that the overall energy requirements increase as the number of steps decrease from five–steps to three–steps. Efficiencies calculated from simulation results show that the four and five–step cycles perform closely with 39% and 42%, respectively. The three–step cycle has a much lower efficiency, even though the theoretical calculations imply that the efficiency should also be close to that of the four and five–step cycles. The five–step reaction cycle has the highest capital requirements at US$370 million due to more equipment and the three–step cycle has the lowest requirement at US$ 275 million. Payback analysis and net present value analysis indicate that the hydrogen costs are highest for the three–step cycle at between US$3.53 per kg for a 5–10yr payback analysis and the five–step cycle US$2.98 per kg for the same payback period.
Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

Master of Science
Department of Chemical Engineering
Larry Erickson
Oxy-fired boilers are receiving increasing focus as a potential response to reduced boiler emissions limits and greenhouse gas legislation. Among the challenges in cleaning boiler gas for sequestration is attaining the necessary purity of the CO[subscript]2. A key component in the oxy-fired cleaning path is high purity SO[subscript]x and NO[subscript]x removal, often through absorption using the lead-chamber or similar process. Aerosol formation has been found to be a source of product contamination in many flue gas absorption processes. A number of authors presented simulation methods to determine the formation of aerosols in gas absorption. But these methods are numerically challenging and not suitable for day-to-day analysis of live processes in the field. The goal of this study is to devise a simple and practical method to predict the potential for and effect of aerosol formation in gas absorption using information from Aspen Plus, a commonly used process simulation tool. The NO[subscript]x absorber in an oxy-fired boiler CO[subscript]2 purification system is used as a basis for this investigation. A comprehensive review of available data suitable for simulating NO[subscript]x absorption in an oxy-fired boiler slipstream is presented. Reaction rates for eight reactions in both liquid and vapor phases are covered. These are entered into an Aspen Plus simulation using a RadFrac block for both rate-based and equilibrium reactions. A detailed description of the simulation format is given. The resulting simulation was compared to a previously published simulation and process data with good agreement. An overall description of the aerosol formation mechanism is presented, along with an estimate of expected aerosol nuclei reaching the NO[subscript]x absorption process. A method to estimate aerosol quantities produced based on inlet gas nuclei concentration and available condensable water vapor is presented. To estimate aerosol composition and emissions, an exit gas slipstream is used to equilibrate with a pure water aerosol using an Aspen Plus Equilibrium Reactor block. Changing the composition of the initial aerosol feed liquid suggests that the location of aerosol formation may influence the final composition and emissions.

Orientador: Antonio José de Almeida Meirelles
Texto em português e inglês
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos
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Resumo: A diminuição gradativa das reservas de combustíveis fósseis e a crescente preocupação com os efeitos do aquecimento global vêm impulsionando cada vez mais as pesquisas por fontes de energia limpa. Dentre essas energias, o etanol de cana-de-açúcar, utilizado no Brasil desde a criação do Programa Nacional do Álcool (PROALCOOL) em 1975, vem se consolidando cada vez mais e sofrendo modificações contínuas no seu processo produtivo. Essas modificações se devem,entre outros aspectos, ao surgimento do conceito de biorrefinaria, que visa um aproveitamento integral da biomassa da cana para produção de energia, e ao rápido e contínuo crescimento da indústria alcoolquímica brasileira, utilizando o etanol como matéria prima para a produção de diversos outros produtos,aumentando a demanda por etanol de melhor qualidade e impulsionando pesquisas no melhoramento do processo produtivo atual. Tendo em conta esse atual cenário, essa tese tem por objetivo estudar o processo de destilação alcoólica industrial, por simulação computacional, analisando a influência dos diversos contaminantes do fermentado de cana no funcionamento das colunas de destilação, investigando a possibilidade do desenvolvimento de uma nova planta industrial para a produção de álcool carburante e álcool neutro, um tipo especial de álcool de alto valor agregado com baixo teor de contaminantes utilizado na indústria de química fina e de bebidas. Para o cumprimento desse objetivo, esta tese está dividida em 6 capítulos: o Capítulo 1 apresenta uma revisão bibliográfica da produção científica associada à produção de álcool combustível, apontando as principais lacunas inerentes a esse tema; o Capítulo 2 discute a produção industrial de cachaça por sistema contínuo apresentando um cuidadoso estudo do equilíbrio de fase dos principais componentes do fermentado de cana de açúcar e analisando a influência dos mesmos no processo produtivo; o Capítulo 3 e o Capítulo 4 apresentam o estudo do processo de produção de álcool hidratado combustível discutindo a influência dos componentes do vinho no funcionamento das colunas, técnicas de otimização de processo aplicadas a um processo industrial real e técnicas de controle de processo aplicadas ao controle de acetaldeído e da graduação alcoólica no bioetanol; o Capítulo 5 apresenta uma nova planta industrial para produção de álcool neutro e álcool hidratado discutindo detalhadamente as vantagens e desvantagens do novo processo frente a plantas industriais tradicionais brasileira e francesa; por fim, o Capítulo 6 apresenta as conclusões gerais do trabalho sugerindo temas para investigações futuras. A análise dos resultados obtidos permitiu conluir que, ainda que consolidado, o processo produtivo de etanol através de cana-de-açúcar apresenta lacunas importantes, principalmente quando se deseja produzir etanol de qualidade superior. Nesse sentido, uma nova planta industrial foi proposta com o objetivo de produzir etanol neutro e hidratado em uma única instalação com redução nos custos de instalação (menor numero de colunas) e de consumo de vapor
Abstract: The gradual reduction of fossil fuel reserves and growing concerns about the effects of global warming have encouraged more research on clean energy sources. Among these energies, ethanol from sugar cane, used in Brazil since the creation of the National Alcohol Program (PROALCOOL) in 1975, has undergone continuous changes in their production process. These changes were due to the emergence of the concept of biorefineries, aiming at a full utilization of sugarcane biomass for energy production, and the continuous and quick growth of the Brazilian alcohol-chemical industry, using the ethanol as raw material for the production of several other products, increasing the demand for ethanol with better quality and boosting the research to improving the current production process.Taking into account this present scenario, this thesis aims to study an industrial process for ethanol production, by computational simulation, analyzing the influence of the contaminants of the fermented sugar cane in the operation of distillation columns, investigating the possibility of developing a new plant for the industrial production of fuel alcohol and neutral alcohol, a particular type of hydrated alcohol of high economic value and low content of contaminants used in the manufacture of fine chemicals and beverages. To fulfill this objective, this thesis is divided into six chapters: Chapter 1 presents a literature review of scientific literature related to the production of fuel alcohol, pointing out the main shortcomings inherent in this theme; Chapter 2 discusses an industrial process for cachaça production by continuous distillation featuring a careful study of the phase equilibrium of the main components of the fermented sugar cane and analyzing their influence in the production process; Chapter 3 and Chapter 4 presents the study of an industrial plant for hydrated fuel ethanol production discussing the influence of the main components of the wine in the columns operation, techniques of process optimization applied to a real industrial process and techniques of control process applied to the control of acetaldehyde and alcoholic graduation in bioethanol; Chapter 5 presents a new plant for neutral and hydrated alcohol productions, discussing in detail the advantages and disadvantages of the new process compared to traditional Brazilian and French industrial plants; finally, the Chapter 6 presents the overall findings of the study and suggesting topics for future investigations. Taking into account the results of this thesis, was possible to concluded that, although consolidated, the ethanol production process using sugar cane as raw material presents important gaps especially when related with high quality ethanol. Some of these shortcomings were solved by proposing a new industrial configuration in order to produce neutral and hydrated ethanol in a single installation with lower installation costs (less number of columns) and steam consumption
Doutorado
Engenharia de Alimentos
Doutor em Engenharia de Alimentos

Orientadores: Maria Regina Wolf Maciel, Betânia Hoss Lunelli
Tese (doutorado) ¿ Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: A produção de biocombustíveis a partir da biomassa apresenta-se como uma alternativa para suprir as limitadas reservas de petróleo. A biomassa, atualmente, está sendo usada para diferentes processos termoquímicos, entre os quais a gaseificação é o de maior destaque. A gaseificação produz gás de síntese que é uma mistura, principalmente, de CO, H2 e CO2. Este gás serve para produzir energia, diferentes produtos químicos e biocombustíveis, como por exemplo, o bioetanol. A partir do gás de síntese, a produção de bioetanol pode ser realizada usando catalisadores químicos ou biocatalisadores, sendo este último processo conhecido como fermentação do gás de síntese. Para o processo integrado de gaseificação da biomassa e posterior fermentação para produção de bioetanol, as informações na literatura são escassas, o que dificulta avaliar a viabilidade desta nova tecnologia, em termos de condições operacionais. O uso de modelos matemáticos e sua simulação computacional podem auxiliar neste estudo. A literatura dispõe de vários estudos envolvendo simulações computacionais aplicadas à gaseificação de diferentes biomassas. Porém, poucos abordam a caracterização real do processo e as propriedades da biomassa utilizada, considerando apenas as propriedades para o carvão mineral, o que acaba gerando divergência nos resultados. Além disso, a maioria fundamenta suas simulações em modelos simples com base na caracterização elementar-imediata, que acaba limitando o desenvolvimento de plantas virtuais, que são baseadas na análise composicional da biomassa quando focadas na produção de bioetanol como etapa final ou como integração do processo. Assim, este trabalho tem como objetivos estudar o processo completo de gaseificação e realizar um estudo preliminar da fermentação do gás de síntese, mediante simulações computacionais, para definir as melhores condições e variáveis que afetam o processo global quando o bagaço de cana-de-açúcar é utilizado como matéria-prima. As simulações foram desenvolvidas utilizando o simulador comercial Aspen Plus¿ e os resultados validados com dados experimentais da literatura e dados obtidos nos Laboratórios LDPS/LOPCA/BIOEN/FEQ/UNICAMP. Para a completa simulação do processo, várias etapas foram estudadas e divididas para melhor entendimento. Foram desenvolvidos modelos matemáticos para predizer propriedades necessárias para o desenvolvimento de processos termoquímicos. Simulações baseadas nas análises elementar-imediata e composicional da biomassa foram realizadas para definir a decomposição inicial da biomassa, demonstrando os diferentes rendimentos e produtos que são gerados e que são a base da etapa inicial da gaseificação. Simulações completas da gaseificação foram desenvolvidas para estudar a gaseificação em diferentes tipos de reatores. A influência das condições de operação na gaseificação como temperatura, razão de equivalência (ER), injeção de vapor e temperatura do pré-aquecedor do ar no desempenho do gaseificador foram avaliadas. Com as condições operacionais da gaseificação definidas foi proposta uma simulação para representar a fermentação do gás de síntese. A partir dos resultados obtidos foi constatado que a composição do gás de síntese é alterada pelo aumento do ER e pela injeção de vapor no processo, e diferentes concentrações de bioetanol são obtidas quando a pressão de entrada do gás de síntese é alterada
Abstract: The production of biofuels from biomass is presented as an alternative to save the limited oil reserves. Currently, biomass is being used for different thermochemical processes, including gasification which is the most prominent. Gasification produces synthesis gas which is a mixture mainly of CO, H2 and CO2. This gas is used to produce energy, several chemicals and biofuels, such as ethanol. The ethanol from synthesis gas may be produced using chemical catalysts or biocatalysts, this latter process is known as fermentation of syngas. The information in the literature is scarce for the integrated gasification of biomass and subsequent fermentation to produce ethanol, making it difficult to see the feasibility of this new technology, in terms of operating conditions. The use of mathematical models and their computer simulation can help this study. Typically, numerous studies involving computer simulations, applied to different biomass gasification, are found in the literature. However, few of them approach the real characterization of process and properties for used biomass, considering only the properties for coal, which ends up generating divergence in the results. Moreover, most of the simulations are grounded on simple models based on proximate-ultimate characteristics, which end up limiting the development of virtual plants, which are based on biomass compositional analysis when focused on the production of ethanol as the final step or as integration process. Thus, the aims of this work are to study the complete gasification process and to carry out a preliminary study of synthesis gas fermentation, through computer simulations, in order to define the best conditions and variables that affect this global process when sugarcane bagasse is used as raw material. The simulations were developed using Aspen Plus ¿ simulator and the results validated with experimental data from literature and data obtained in the laboratories LDPS / LOPCA / BIOEN / FEQ / UNICAMP. For the full simulation of the process, several steps were studied and divided for a better understanding. Mathematical models were developed to predict properties required for the development of thermochemical processes. Simulations based on biomass analysis as proximate-ultimate and compositional were done to define the initial decomposition of biomass, demonstrating the different yields and products that are generated and which are the basis of the initial stage of the gasification. Complete simulations of gasification were carried out to study different types of gasification reactors. The influence of operating conditions at gasification performance was investigated; variables such as temperature, equivalence ratio (ER), steam injection and preheater temperature were evaluated. With the set conditions of gasification was proposed a simulation to represent the fermentation of syngas. It was demonstrated that the synthesis gas composition is changed when increased the ER and steam injection; and different ethanol concentrations are obtained when the input pressure of the synthesis gas is changed
Doutorado
Desenvolvimento de Processos Químicos
Doutora em Engenharia Quimica

Accurate modeling of mixed solvent electrolyte systems is difficult and is not readily available in property modeling software such as Aspen Plus. Support for modeling these systems requires the knowledge and input of parameters specific to the compounds in question. The need for these parameters is particularly relevant in simulating new designs based upon recent developments in a concept known as pass-through distillation (PTD). In support of a specific application of PTD, this work determines and validates with existing experimental data, accurate user-parameters for the eNRTL property model in the ternary system of ethanol, water, and lithium bromide. Furthermore, this work creates the foundation for simulating this new PTD process by modeling the removal of bioethanol from a fermentation broth using low temperature evaporation in conjunction with absorption and stripping units to omit the need of a condenser requiring refrigeration. This will enable future investigations into the applications of PTD as well as provide a foundation for modeling the ternary system of ethanol, water and lithium bromide.

Les risques sont inhérents à l’activité industrielle. Les prévoir et les maîtriser sont essentiels pour la conception et la conduite en sécurité des procédés. La réglementation des risques majeurs impose aux exploitants la réalisation d’études de sécurité quantitatives. La stratégie de maîtrise des risques repose sur la pertinence des analyses de risques. En marche dégradée, la dynamique des événements est déterminante pour quantifier les risques. Toutefois, de nos jours cette connaissance est difficilement accessible. Ce travail propose une méthodologie d’analyse de risques quantitative qui combine la méthode HAZOP, le retour d’expérience et la simulation dynamique de dérives de procédés. Elle repose sur quatre grandes étapes : La première étape est l’étude du fonctionnement normal du procédé. Pour cela, le procédé est décrit de façon détaillée. Des études complémentaires de caractérisation des produits et du milieu réactionnel sont menées si nécessaires. Ensuite, le procédé est simulé dynamiquement en fonctionnement normal. Lors de la seconde étape, parmi les dérives définies par l’HAZOP et le retour d’expérience, l’analyste discrimine celles dont les conséquences ne sont pas prévisibles et/ou nécessitent d’être quantifiées. La troisième phase fournit une quantification du risque sur la base de la simulation dynamique des scenarii retenus. Lors de la dernière étape, des mesures de maîtrise des risques sont définies et ajoutées au procédé lorsque le niveau de risque est supérieur au risque tolérable. Le risque résiduel est ensuite calculé jusqu’à l’atteinte de la cible sécurité. Le logiciel Aspen Plus Dynamics est sélectionné. Trois études de cas sont choisies pour démontrer d’une part, la faisabilité de la méthodologie et d’autre part, la diversité de son champ d’application : · la première étude de cas porte sur un réacteur semi-continu siège d’une réaction exothermique. L’oxydation du thiosulfate de sodium par le peroxyde d’hydrogène est choisie. Ce cas relativement simple permet d’illustrer la diversité des causes pouvant être simulées (erreur procédurale, défaut matériel, contamination de produits, …) et la possibilité d’étudier des dérives simultanées (perte de refroidissement du milieu et sous dimensionnement de la soupape de sécurité). · le deuxième cas concerne un réacteur semi-batch dans lequel une réaction exothermique de sulfonation est opérée. Elle est particulièrement difficile à mettre en œuvre car le risque d’emballement thermique est élevé. Cette étude montre l’intérêt de notre approche dans la définition des conditions opératoires pour la conduite en sécurité. · le troisième cas d’étude porte sur un procédé continu de fabrication du propylène glycol composé d’un réacteur et de deux colonnes de distillation en série. L’objectif est ici d’étudier la propagation de dérives le long du procédé. Sur la base du retour d’expérience, deux dérives au niveau du rebouilleur de la première colonne sont étudiées et illustrent les risques de pleurage et d’engorgement. La simulation dynamique illustre la propagation d’une dérive et ses conséquences sur la colonne suivante.

This thesis focuses on enhancing knowledge on co-firing oxy-combustion cycles to boost development of this valuable technology towards the aim of it becoming an integral part of the energy mix. For this goal, the present work has addressed the engineering issues with regards to operating a retrofitted multi-fuel combustor pilot plant, as well as the development of a rate-based simulation model designed using Aspen Plus®. This model can estimate the gas composition and adiabatic flame temperatures achieved in the oxy-combustion process using coal, biomass, and coal-biomass blends. The fuels used for this study have been Daw Mill coal, El Cerrejon coal and cereal co-product. A parametric study has been performed using the pilot-scale 100kWth oxy-combustor at Cranfield University and varying the percentage of recycle flue gas, the type of recycle flue gas (wet or dry), and the excess oxygen supplied to the burner under oxy-firing conditions. Experimental trials using co-firing with air were carried out as well in order to establish the reference cases. From these tests, experimental data on gas composition (including SO3 measurement), temperatures along the rig, heat flux in the radiative zone, ash deposits characterisation (using ESEM/EDX and XRD techniques), carbon in fly ash, and acid dew point in the recycle path (using an electrochemical noise probe), were obtained. It was clearly shown during the three experimental campaigns carried out, that a critical parameter was that of minimising the air ingress into the process as it was shown to change markedly the chemistry inside the oxy-combustor. Finally, part of the experimental data collected (related to gas composition and temperatures) has been used to validate the kinetic simulation model developed in Aspen Plus®. For this validation, a parametric study considering the factor that most affect the oxy-combustion process (the above mentioned excess amount of air ingress) was varied. The model was found to be in a very good agreement with the empirical results regarding the gas composition.

Orientador: Rubens Maciel Filho, Maria Regina Wolf Maciel
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: Este trabalho de tese propôs um processo para a produção de acetato de etila através da reação de esterificação do ácido acético com o etanol, utilizando conceitos de intensificação de processos e de Engenharia Verde (Zero Avoidable Pollution com renweable feedstock). A contribuição principal desta pesquisa é a proposta de uma planta conceitual com alta pureza de todas as correntes do processo, o que diminui desperdícios, de modo que o produto indesejado ou os reagentes não convertidos não estejam presentes nas correntes de saída do sistema. No processo proposto, todos os reagentes são de origem renovável. O acetato de etila é um solvente orgânico importante utilizado na produção de vernizes, de tintas, de resinas sintéticas e de agentes adesivos, sendo produzido normalmente, através da reação reversível do ácido acético com o etanol, com ácido sulfúrico com catalisador. O processo deste sistema de obtenção é bastante complexo porque o produto (acetato de etila) não é o componente mais volátil nem o menos volátil no sistema, de modo que a etapa de separação não é fácil de definir. O projeto conceitual proposto inclui um reator de tanque contínuo (CSTR) acoplado a um retificador, um decantador e duas colunas de purificação, para a água e o acetato de etila. O software comercial ASPEN PLUS® foi utilizado para a realização dos estudos do processo proposto através de simulação computacional em estado estacionário, e o simulador ASPEN DYNAMICS® foi utilizado para a simulação dinâmica
Abstract: This work proposes a process for ethyl acetate production via esterification of acetic acid with ethanol using concepts of process intensification and zero avoidable pollution. The main contribution of this work is the high-purity of all process streams, including the wastes ones, so that undesired product or unconverted reactants are not present in any throughput streams. Ethyl acetate is an important organic solvent widely used in the production of varnishes, ink, synthetic resins, and adhesive agents and it is normally produced via reversible reaction of acetic acid with ethanol, with sulfuric acid as catalyst. The process design of such system is complex because the ethyl acetate product is neither the lightest nor the heaviest component in the system, so that the separation stage is not an easy task. The proposed process design includes a continuous-stirred tank reactor (CSTR) coupled with a rectifier, a decanter and two purification columns for water and ethyl acetate. The commercial ASPEN PLUS® software was used to steady state simulation and ASPEN DYNAMICS® was used to dynamic simulation
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química

Orientador: Rubens Maciel Filho
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Esta tese apresenta um estudo de estratégias de esquemas de controle em unidades de destilação a vácuo de refinarias de petróleo, com o uso de dados e informações de uma refinaria brasileira, de modo a se desenvolver uma simulação representativa do processo, onde uma diferença global máxima de 5% entre os resultados de simulação e os dados de saída reais foi obtida. A simulação foi executada com alto nível de detalhamento, com cálculos de queda de pressão, dimensionamento de sistemas de bombeamento e uso de internos de coluna comerciais. Uma análise paramétrica foi executada para a verificação das variáveis mais influentes do processo. A simulação em estado estacionário resultante foi então convertida para o regime dinâmico, onde um esquema de controle equivalente ao esquema de controle da planta real foi implementado. Este esquema de controle foi submetido a um conjunto de perturbações usuais ao processo real, produzindo respostas dinâmicas do processo para cada perturbação aplicada. Pela análise das dinâmicas destas respostas e das respostas do sistema em malha aberta, um esquema de controle alternativo foi proposto e verificado da mesma maneira que o esquema de controle equivalente. Malhas de controle específicas para quantificar a qualidade dos produtos, tendo por base o índice ASTM D86 foram inseridas. A comparação entre os dois esquemas de controle por meio das respostas dinâmicas na qualidade dos produtos, considerando como parâmetro o ISE (Integral Squared Error) das malhas de cada esquema para comparação, apresentou uma redução média do erro em 70% na qualidade dos produtos principais
Abstract: A petroleum vacuum distillation unit study on control scheme strategies is developed in this work. Real plant data and information is gathered from a Brazilian Refinery to develop a representative simulation of the process, which had achieved a maximum 5% overall difference from the plant results. The simulation was set to be highly detailed, including pressure drop calculations, pumping system and the use of commercial column internals (packing and plates) in it. A parametric analysis was carried in order to verify the most influent variables in the process, with respect to temperature profiles, product flows and product qualities. The resultant steady state simulation was then converted into dynamic regime, when a control scheme equivalent to the real plant control scheme was implemented. This control scheme was then subjected to a set of common perturbations that occur in the real process, producing the dynamic response of the process to each perturbation applied. By analyzing the dynamics of these responses and the open loop responses, an alternative control scheme is proposed and verified in the same manner the later one was. A specific control loop was proposed to account a petroleum product quality index, such as ASTM D86 95% recovery. The comparison of the control schemes by means of the dynamic responses considering the correlated ISE (integral squared error) of each scheme has shown an average error reduction of 70% in the main products quality
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química

ASPEN-Plus se utilizó para llevar a cabo investigaciones en régimen estacionario sobre una máquina comercial de refrigeración de absorción de 3 toneladas (10 kW de capacidad de refrigeración) accionada con gas natural y un refrigerador de difusión-absorción (DAR) de pequeña potencia (7.5 W de capacidad de refrigeración).Antes de iniciar las simulaciones, se selecciona entre los nueve modelos implementados en la librería de ASPEN-Plus, el modelo adecuado para estimar las propiedades termodinámicas del fluido de trabajo amoníaco/agua en amplios rangos de temperatura (273,16 ≤ T ≤ 613,15 K) y de presión (0 < P ≤ 210 bar). Se ha demostrado que la ecuación de estado de Peng-Robinson-Boston-Mathias (PR-BM) es la más adecuada para el par de trabajo amoníaco/agua en los intervalos de temperatura y presión típicos en las máquinas de refrigeración de absorción. Los modelos de simulación desarrollados en ASPEN-Plus para las máquinas de refrigeración de absorción, reproducen y predicen bastante bien los resultados experimentales. Los primeros ensayos experimentales del refrigerador comercial de difusión-absorción (DAR) han mostrado que se requiere un suministro de calor al generador superior a 35W para garantizar el funcionamiento de la máquina y su estabilidad. Además, todas las características esenciales del refrigerador han sido determinadas experimentalmente, especialmente los coeficientes globales de transferencia de calor de la cámara refrigerada y el evaporador, las cuales son(UA)_cab=0.554 WK^(-1) and (UA)_int=0.3 WK^(-1), respectivamente. El mejor rendimiento del refrigerador ha sido obtenido experimentalmente con una fuente de alimentación eléctrica de 46W y una temperatura del generador de 167°C. Se ha encontrado que el COP de la máquina es de 0.159. Las predicciones de los modelos ASPEN-Plus del DAR han mostrado una buena concordancia con los datos experimentales. Por último, un modelo dinámico de caja negra ha sido desarrollado para el refrigerador de difusión-absorción (DAR) en el entorno de Matlab Simulink®. Se ha encontrado que la función de transferencia de primer orden con retardo describe correctamente la relación entre la potencia de accionamiento en el generador y la capacidad de refrigeración.
ASPEN-Plus was used to carry out steady-state investigations on a commercial 3-ton gas-fired absorption chiller (10 kW cooling capacity) and a small capacity (7.5W cooling capacity) diffusion-absorption refrigerator (DAR). Before starting the simulations, the adequate thermodynamic properties model for the ammonia/water fluid mixture over wider ranges of temperature (273.16 ≤ T ≤ 613.15 K) and pressure (0 < P ≤ 210 bar) was selected among nine candidates from the ASPEN-Plus model library. It was found that the Peng-Robinson-Boston-Mathias equation of state (PR-BM) is the most suitable for the ammonia/water working pair in the temperature and pressure ranges encountered in absorption refrigerating machines. The ASPEN-Plus simulation models developed for the absorption chiller were able to reproduce and predict quite well the experimental findings. First experimental tests on the commercial diffusion-absorption refrigerator showed that a heat supply of greater than 35 W in the generator is required to ensure the functioning of the machine and its stability. Further, all the essential features of the refrigerator were determined experimentally, especially the overall heat transfer coefficients of the refrigerated room cabinet and the evaporator, which were (UA)_cab=0.554 WK^(-1) and (UA)_int=0.3 WK^(-1), respectively. The best performance of the refrigerator was reached experimentally with an electric power supply of 46 W and a generator temperature of 167°C. The machine COP was found to be 0.159. The predictions of the ASPEN-Plus models of the DAR showed good agreement with the experimental data. Finally, a dynamic black-box model was developed for the diffusion-absorption refrigerator (DAR) using Matlab Simulink® environment. It was found that a first order transfer function with delay describes correctly the relationship between the power input to the generator and the cooling capacity. The unsteady-state behavior of the refrigerator predicted by the black-box developed agreed well with the experimental data.

Le développement du bois énergie est un des principaux leviers dans la lutte contre le changement climatique. Cependant son utilisation à grande échelle n’est pas sans risque pour l’environnement. Afin de quantifier les impacts environnementaux de la filière bois énergie, nous avons, dans un premier temps, développé un modèle systémique de la filière, depuis la forêt jusqu’à la production d’énergie. Deux technologies ont été considérées pour la co-production d’électricité et de chaleur à partir de biomasse forestière : l’une, traditionnelle, par combustion directe, et l’autre, plus avancée mais moins mature, par gazéification. Dans le cas de la gazéification, nous avons défini les conditions opératoires les plus favorables du procédé en tenant compte des rendements énergétiques et exergétiques ainsi que de la qualité du syngas. Dans un deuxième temps, nous avons calculé les flux de carbone et de minéraux exportés lors de la récolte du bois ainsi que le nombre d’hectares requis, puis les ressources et rejets liées au fonctionnement des centrales biomasses. Nous avons noté qu’une intensification des pratiques sylvicoles résultait en une augmentation des exportations de minéraux. Enfin, nous avons évalué les performances environnementales des deux filières à l’aide d’une Analyse de Cycle de Vie (ACV). Dans le contexte énergétique français, les deux systèmes offrent des performances très similaires, avec un léger avantage à la combustion. Du point de vue du changement climatique, il serait plus particulièrement bénéfique de développer ces procédés biomasse afin de remplacer les technologies de production d’énergie basées sur les combustibles fossiles
Biomass is one of the most promising renewable energy source in Europe. Its use as a substitute to fossil energy is expected to mitigate climate change. However, potential drawbacks are also feared with large scale development. In order to assess the environmental impacts of the biomass-to-energy chain, we firstly developed a model of the bioenergy system, from the forest to the energy production. We focused on two biomass power plants for combined heat and power (CHP) production: one is based on the conventional direct combustion process while the other is based on the more advanced gasification process. Gasification offers higher electrical efficiency, but its development is still facing technical difficulties. In case of the gasification process, we defined the best operating conditions regarding energetic and exergetic efficiencies, as well as the syngas quality requirements. Secondly, we calculated the carbon and mineral flows taken from the forest through energy wood harvesting, along with the forested area required to feed the CHP plant. The other resources and emissions related to the plant operation were also predicted. We observed that more extensive forestry practices led to an increase in the mineral exports. Finally, we evaluated the environmental performance of the two biomass CHP plants using life cycle assessment (LCA). Within French energy context, we found that both CHP technologies had very similar impacts with a slight advantage toward the combustion process. It appears of particular benefit to replace current fossil energy systems with biomass CHP plants to reduce climate change

The change in climate as a consequence of anthropogenic activities is a subject ofmajor concerns. In order to reduce the amount of greenhouse gas emissions inthe atmosphere, the utilization of renewable, fossil-free power generationapplications becomes inevitable. Geothermal and solar energy play a major rolein covering the increased demand for renewable energy sources of today’s andfuture’s society. A special focus hereby lies on the Concentrating Solar Powertechnologies and different geothermal concepts. The costs for producingelectricity through Concentrating Solar Power and therefore Parabolic Trough Collectorsas well as geothermal conversion technologies are still comparatively high. Inorder to minimize these expenses and maximize the cycle’s efficiency, thepossible synergies of a hybridization of these two technologies becomeapparent. This thesis therefore investigates the thermodynamic and economicbenefits and drawbacks of this combination from a global perspective. For that,a Parabolic Trough Collector system is combined with the geothermal conversionconcepts of Direct Steam, Single and Double Flash, Organic Rankine as well asKalina Cycles. The solar integrations under investigation are Superheat,Preheat and Superheat & Reheat of the geothermal fluid. The thermodynamicanalysis focuses on the thermal and utilization efficiencies, as well as therequired Parabolic Trough Collector area. The results indicate that in the caseof the Superheat and Superheat & Reheat setup, the thermal efficiency canbe improved for all geothermal concepts in comparison to their correspondinggeothermal stand-alone case. The Preheat cases, with the major contributionfrom solar energy, are not able to improve the cycle’s thermal efficiencyrelative to the reference setup. From an exergy perspective the findings varysignificantly depending on the applied boundary conditions. Still, almost allcases were able to improve the cycle’s performance compared to the referencecase. For the economic evaluation, the capital investment costs and thelevelized costs of electricity are studied. The capital costs increasesignificantly when adding solar energy to the geothermal cycle. The levelizedelectricity costs could not be lowered for any hybridization case compared tothe reference only-geothermal configurations. The prices vary between20.04 €/MWh and 373.42 €/MWh. When conducting a sensitivity analysison the solar system price and the annual mean irradiance, the Kalina Superheatand Superheat & Reheat, as well as the Organic Rankine Preheathybridizations become cost competitive relative to the reference cases.Concluding, it is important to remark, that even if the hybridization of the ParabolicTrough and the different geothermal concepts makes sense from a thermodynamicperspective, the decisive levelized costs of electricity could not be improved.It is, however, possible that these costs can be further reduced under speciallocal conditions, making the addition of Parabolic Trough solar heat tospecific geothermal concepts favorable.

Biofuels produced from lignocellulosic biomass via the fermentation platform are sustainable energy alternatives to fossil fuels. Process Systems Engineering (PSE) uses computer-based tools and methods to design, simulate and optimize processes. Application of PSE tools to the design of economic biorefinery processes requires the development of simulation approaches that can be integrated with existing, mature PSE tools used to optimize traditional refineries, such as Aspen Plus. Current unit operation models lack the ability to describe unsteady state fermentation processes, link unsteady state fermentation with in situ separations, and optimize these processes for competing factors (e.g., yield and productivity). This work applies a novel architecture of commercial PSE tools, Aspen Plus and MATLAB, to develop techniques to simulate time-dependent fermentation without and with in situ separations for process design, analyses and optimization of the operating conditions. Traditional batch fermentation simulations with in situ separations decouple these interdependent steps in a separate “steady state” reactor followed by an equilibrium separation of the final fermentation broth. A typical mechanistic system of ordinary differential equations (ODEs) describing a batch fermentation does not fit the standard built-in power law reaction kinetics model in Aspen Plus. To circumvent this challenge, a novel platform that links the batch reactor to a FORTRAN user kinetics subroutine (incorporates the ODEs) combined with component substitution (to simulate non-databank components) is utilized to simulate an unsteady state batch and in situ gas stripping process. The resulting model system predicts the product profile to be sensitive to the gas flow rate unlike previous “steady state” simulations. This demonstrates the importance of linking a time-dependent fermentation model to the fermentation environment for the design and analyses of fermentation processes. A novel platform linking the genetic algorithm multi-objective and single-objective optimizations in MATLAB to the unsteady state batch fermentation simulation in Aspen Plus through a component object module communication platform is utilized to optimize the operating conditions of a typical batch fermentation process. Two major contributions are: prior concentration of sugars from a typical lignocellulosic hydrolysate may be needed and with a higher initial sugar concentration, the fermentation process must be integrated with an in situ separation process to optimize the performance of fermentation processes. With this framework, fermentation experimentalists can use the full suite of PSE tools and methods to integrate biorefineries and refineries and as a decision-support tool to guide the design, analyses and optimization of fermentation-based biorefineries.

La production du biogaz ne cesse d’augmenter dans le monde entier. La combustion pour produire de la chaleur et de l’électricité, de même que la production du biométhane pour l’injection au réseau de gaz de ville sont les deux applications industrielles majeures du biogaz. La recherche actuelle sur la valorisation du biogaz se focalise sur la production des produits à haute valeur ajoutée comme l’hydrogène pour la mobilité. C’est l’objectif principal du projet VABHYOGAZ3, financé par ADEME, qui vise à déployer la production d’H2 à partir du biogaz dans le Tarn. Le procédé de reformage du biogaz adopté par les partenaires industriels du projet VABHYOGAZ3 est le vaporeformage, qui est couramment utilisé dans l’industrie pour reformer le gaz naturel, et qui est un procédé fortement énergivore. Cette thèse a pour objectif de développer des catalyseurs performants pour le reformage à sec du méthane (RSB : conversion de CH4 et CO2 en syngas – mélange de CO et H2) et pour le tri-reformage du méthane (Tri-RB : conversion de CH4, CO2, H2O et O2 en syngas). Le but ultime est d’optimiser l’efficacité énergétique du procédé global de la production d’H2 via le reformage du biogaz, qui est indispensable pour rendre ce procédé économiquement viable. En fait, les catalyseurs en RSB et Tri-RB ont souvent le problème de désactivation catalytique en raison du dépôt de coke et du frittage thermique à haute température (> 700°C). L’obtention d’un catalyseur performant sous les conditions sévères de RSB et Tri-RB est crucial pour le déploiement de ces procédés à large échelle industrielle. Dans un premier temps, une étude sur la thermodynamique des procédés globaux de la production d’H2 via le reformage du biogaz a été effectuée. Les bilans de matière et d’énergie de ces procédés ont aussi été réalisés par la simulation sur Aspen Plus. Ensuite, différents catalyseurs à base de nickel supporté sur les supports d’hydroxyapatite (HAP) et d’hydroxyapatite substituée au Mg (Mg_HAP) ont été préparés et caractérisés. Les supports à base d’HAP sont considérés comme des nouveaux matériaux catalytiques qui ont des propriétés appropriées en catalyse hétérogène, en particulier pour des procédés à haute température tels que RSB et Tri-RB. Dans cette étude, les supports HAP ayant les rapports molaires de Ca/P de 1,55, 1,67 et 1,75, et Mg_HAP (substitution de 2,2, 5,8 et 8,5% de Ca par Mg) ont été synthétisés. Ces supports ont été dopés avec 5% en masse de Ni par imprégnation à sec. Ces catalyseurs ont été évalués dans les deux réactions de RSB et Tri-RB dans un réacteur à lit fixe. Une étude paramétrique sur l’influence des conditions opératoires incluant la température, la pression totale, le débit d’alimentation du biogaz, et le rapport molaire de la vapeur d’eau sur méthane (S/C) et d’oxygène sur méthane (O/C), a été effectuée. L’objectif a été de comparer et d’identifier les meilleurs catalyseurs et les meilleurs conditions opératoires. Les bilans de matières ont été établis. Les raisons de la désactivation catalytique ont été mises en évidence. Enfin, la stabilité catalytique des meilleurs catalyseurs a été étudiée pendant 150-300 h de réaction. Les résultats obtenus montrent que les catalyseurs à base de Ni supporté sur HAP ou Mg_HAP sont compétitifs par rapport aux meilleurs catalyseurs identifiés dans la littérature. Ce travail confirme également l’intérêt de l’utilisation des nouveaux supports à base d’HAP dans la catalyse hétérogène et en particulier dans les procédés à haute température
Biogas production worldwide is increasing steadily. The combustion to generate heat and electricity, and the biomethane production for injection into the city gas grid are currently the two major industrial applications of biogas. Current research on biogas valorization targets the production of high-value products such as hydrogen for transportation. This is the main objective of the VABHYOGAZ3 project funded by ADEME, which aims at deploying the production of H2 from biogas in the Tarn department, France. Biogas steam reforming, adopted by the industrial partners of the VABHYOGAZ3 project, is a commonly used process in the industry to reform natural gas, but it is a highly energy-consuming process. This PhD thesis aims to develop efficient catalysts for the Dry Reforming of Methane (DRM: conversion of CH4 and CO2 into syngas - mixture of CO and H2) and for the Tri-Reforming of Biogas (Tri-RB: conversion of CH4, CO2, H2O and O2 into syngas). The ultimate goal was to optimize the energy efficiency of the overall process of H2 production through the reforming of biogas, which is essential to make the process economically viable. In fact, DRM and Tri-RB catalysts usually have the problem of catalytic deactivation due to coke deposition and thermal sintering at high temperature (> 700 °C). Obtaining an efficient catalyst under severe conditions of DRM and Tri-RM is crucial for the deployment of these processes at large industrial scale. First, a study on the thermodynamics of the overall processes for H2 production via the reforming of biogas was carried out. Mass and energy balances of these processes were also obtained by ASPEN simulation. Then, various nickel-based catalysts supported on hydroxyapatite (HAP) and on hydroxyapatite substituted with Mg (Mg_HAP) were prepared and characterized. HAP-based supports are considered to be new catalytic materials which have suitable properties for heterogeneous catalysis, in particular for high temperature processes such as DRM and Tri-RM. In this study, HAP supports having the Ca/P molar ratio of 1.55, 1.67 and 1.75, and Mg_HAP (substitution of 2.2, 5.8 and 8.5 % of Ca with Mg) have been synthesized. These supports were doped with 5 wt.% of Ni by incipient wetness impregnation method. These catalysts were evaluated for both DRB and Tri-RB reactions in a fixed bed reactor. A parametric study on the influence of operating conditions including temperature, total pressure, biogas feeding rate, and molar ratio of steam to methane (S/C) and oxygen to methane (O/C), has been performed. The objective was to compare and identify the best catalysts and the best operating conditions. Mass balances have been established experimentally. Catalytic deactivation has been discussed and evidenced. Finally, the stability of the best catalysts was studied for a long reaction time of 150-300 h, and catalyst regeneration was also performed. This work shows that Ni-based catalysts supported on HAP or on Mg_HAP are competitive to the best catalysts identified in the literature. This work also confirms the interest of the use of new HAP-based supports in heterogeneous catalysis and particularly in high temperature processes

Les réseaux d'échangeurs de chaleur constituent une partie importante des procédés de transformation de la matière. Au cours des vingt-cinq dernières années, les travaux de recherche dans ce domaine ont connu un essor considérable ; cela s'est traduit par la proposition de méthodes permettant de concevoir de façon optimale de tels réseaux. Cependant, les questions se rapportant au comportement dynamique et au contrôle-commande de procédés industriels comportant un grand nombre d'échangeurs de chaleur ont été souvent négligées. En effet, la conception du réseau d'échangeurs de chaleur se fait habituellement après l'optimisation du procède et indépendamment de celle-ci. Or, la variation des paramètres du procédé a un grand impact sur le procédé lui-même et en particulier sur les apports thermiques au procède (utilités, échanges entre fluides chauds et fluides froids,). Cette étude a pour objectif sur un procédé industriel particulier de définir une méthodologie permettant d'optimiser la conduite d'un procédé industriel complexe en tenant compte simultanément des opérations unitaires du procédé et du réseau d'échangeurs de chaleur. Sur un procédé pétrolochimique complexe, fourni par l'institut français du pétrole, il a été réalisé tout d'abord la recherche d'un réseau d'échangeurs de chaleur par conception optimale, puis il a été envisage la possibilité d'utiliser la simulation dynamique, avec le logiciel SpeedUp, pour étudier le comportement dynamique de l'ensemble (opérations du procédé + réseau d'échangeurs de chaleur) ; la stabilité du procédé face à des perturbations externes a été particulièrement étudiée. A partir de ce modèle du procédé retenu pour simulation dynamique généralisée, il a été possible de proposer une méthodologie permettant l'optimisation en dynamique d'un réseau d'échangeurs de chaleur associé à un procédé industriel complexe.

The waste heat recovery technologies have become very relevant since many industrial plants continuously reject large amounts of thermal energy during normal operation which contributes to the increase of the production costs and also impacts the environment. The simulation programs used in industrial engineering enable development and optimization of the operational processes in a cost-effective way. The company Chematur Engineering AB, which supplies chemical plants in many different fields of use on a worldwide basis, was interested in the investigation of the possibilities for effective waste heat recovery from the hydrogenation of dinitrotoluene, which is a sub-process in the toluene diisocyanate manufacture plant. The project objective was to implement waste heat recovery by application of the Organic Rankine Cycle and the Absorption Refrigeration Cycle technologies. Modeling and design of the Organic Rankine Cycle and the Absorption Refrigeration Cycle systems was performed by using Aspen Plus® simulation software where the waste heat carrier was represented by hot water, coming from the internal cooling system in the hydrogenation process. Among the working fluids investigated were ammonia, butane, isobutane, propane, R-123, R-134a, R-227ea, R-245fa, and ammonia-water and LiBr-water working pairs. The simulations have been performed for different plant capacities with different temperatures of the hydrogenation process. The results show that the application of the Organic Rankine Cycle technology is the most feasible solution where the use of ammonia, R-123, R-245fa and butane as the working fluids is beneficial with regards to power production and pay-off time, while R-245fa and butane are the most sustainable choices considering the environment.

Increasing the efficiency of conventional power plants is a crucial aspect in the quest of reducing the energy consumption of the world and to having sustainable energy systems in the future. Thus, within the scope of this thesis the possible efficiency improvements for the Wärtsilä 18V50DF model gas engine based combine power generation options are investigated by recovering waste heat of the engine via Organic Rankine cycle (ORC).  In order to this, four different ORC models are simulated via Aspen Plus software and these models are optimized for different objective functions; power output and price per unit of electricity generation. These ORC models are: regenerative Organic Rankine cycle (RORC), cascaded Organic Rankine cycle with an economizer (CORCE), cascaded Organic Rankine cycle with two heat sources (CORC2) and cascaded Organic Rankine cycle with three heat sources (CORC3). In the cascaded cycle models there are two loops which are coupled with a common heat exchanger that works as a condenser for the high temperature (HT) loop and as a preheater for the low temperature (LT) loop. By using this common heat exchanger, the latent heat of condensation of the HT loop is utilized. The engine’s hot exhaust gases are used as main heat source in all the ORC models. The engine’s jacket water is utilized in the CORC2 models as an additional heat source to preheat the LT working fluid. In the CORC3 models engine’s lubrication oil together with the jacket water are used as additional sources for preheating the LT loop working fluid. Thus, the suitability of utilizing these two waste heat sources is examined. Moreover, thermodynamic and economic analyses are performed for each model and the results are compared to each other. The effect of different working fluids, condenser cooling water temperatures, superheating on cycles performance is also evaluated. The results show that with the same amount of fuel the power output of the engine would be increased 2200 kW in average and this increases the efficiency of the engine by 6.3 %. The highest power outputs are obtained in CORC3 models (around 2750 kW) whereas the lowest are in the RORC models (around 1800 kW). In contrast to the power output results, energetic efficiencies of the RORC models (around 30 %) are the highest and CORC3 models (around 22 %) are the lowest. In terms of exergetic efficiency, the highest efficiencies are obtained in CORC2 (around 64.5 %) models whereas the lowest in the RORC models (around 63 %). All the models are found economically feasible since thermodynamically optimized models pay the investment costs back in average of 2 years whereas the economically optimized ones in 1.7. The selection of the working fluid slightly affects the thermodynamic performance of the system since in all the ORC configurations Octamethyltrisiloxane (MDM) working fluid cycles achieve better thermodynamic performances than Decamethyltetrasiloxane (MD2M) working fluid cycles. However, the choice of working fluid doesn’t affect the costs of the system since both working fluid cycles have similar price per unit of electricity generation. The CORC2 models obtain the shortest payback times whereas the CORC3 models obtain the longest Thus the configuration of the ORC does affect the economic performance. It is observed from the results that increasing the condenser cooling water temperature have negative impact on both thermodynamic and economic performances. Also, thermodynamic performances of the cycles are getting reduced with the increasing degree of superheating thus superheating negatively affects the cycle’s performances. The engine’s jacket water and lubrication oil are found to be sufficient waste heat sources to use in the ORC models.

Les rejets des Usines à Zinc de Kolwezi contiennent majoritairement du zinc sous forme réfractaire (ferrite) au traitement hydrométallurgique conventionnel. Ils contiennent d’autres métaux « lourds » qui les rendent dangereux vis-à-vis de l’environnement dans lequel ils sont actuellement entreposés. Ces métaux, dont la plupart peuvent être valorisés, font de ces rejets un véritable gisement secondaire. Il est donc impératif de mettre au point un procédé adéquat de valorisation ;d’où le thème de la présente thèse :« Etude de valorisation des rejets des Usines à Zinc de Kolwezi, RDC ».

A l’aide des techniques modernes de caractérisation (physico–chimique, minéralogique et morphologique), nous sommes arrivés à cibler, à adapter et à justifier l’utilisation d’une technique de valorisation des matières minérales existantes. Les minéraux utiles contenus dans les rejets UZK ont été sulfatés par digestion et sélectivement mis en solution après un grillage. La sulfatation s’est avérée l’étape déterminante du procédé et un intérêt particulier a été focalisé sur cette étape en réalisant une étude cinétique approfondie.

Les données et informations récoltées tout le long de cette recherche nous ont permis de réaliser une simulation du procédé par le logiciel ASPEN PLUS. Ce qui a permis de faire une ébauche d’un schéma de traitement industriel. Ce dernier s’est avéré souple vis-à-vis de l’utilisation d’autres matières comme les calcines des concentrés sulfurés cuivre-zinc.

Residues from the Kolwezi Zinc Plant (Usines à Zinc de Kolwezi UZK) essentially contain zinc in a refractory (ferrite) form, which is difficult to recover by conventional hydrometallurgical methods. « Heavy» metals are also present that make them hazardous towards the environment in which they are currently stored. Most of these metals are valuable; thus, the UZK residues are a real secondary deposit. It is therefore imperative to develop an appropriate method of treatment, hence the theme of the present thesis: « Recovery study of values metals from Kolwezi Zinc Plant residues, DRC ».

Using modern techniques of characterization (physical and chemical, mineralogical and morphological), we focused, adapted and justified the use of a technique for efficient recovery of the existing valuable minerals. The minerals contained in UZK residues have been sulphated by digestion and thereafter selectively dissolved after roasting. Sulphatation proved to be the decisive step of the process and a particular attention has been given to this step by performing a detailed kinetic study.

The data and information collected throughout this research allowed a simulation of the developed method by using the « Aspen Plus » software. This allowed us to propose a draft scheme of industrial processing. The latter proved flexible towards the use of other materials such as calcines of copper-zinc sulphide concentrates.

Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished

Yes
This paper presents a simulation study of vacuum membrane distillation (VMD) for desalination. A simulation model was built on Aspen Plus® platform as user defined unit operation for VMD module. A simplified mathematical model was verified and the analysis of process performance based on simulation was also carried out. Temperature and concentration polarization effects are significant in the conditions of higher feed temperature and/or vacuum pressure. The sign of difference of the vapour pressures between at the membrane interfaces, is a pointer of the vacuum pressure threshold. Increasing the vacuum pressure at lower feed temperature is an effective way to increase the permeate flux and reduce the energy consumption simultaneously.

Thermochemical processes for hydrogen production driven by nuclear energy are promising alternatives to existing technologies for large-scale commercial production of hydrogen, without dependence on fossil fuels. In the Copper-Chlorine (Cu-Cl) cycle, water is decomposed in a sequence of intermediate processes with a net input of water and heat, while hydrogen and oxygen gases are generated as the products. The Super Critical Water-cooled Reactor (SCWR) has been identified as a promising source of heat for these processes. In this thesis, the process analysis and simulation models are developed using the Aspen PlusTM chemical process simulation package, based on experimental work conducted at the Argonne National Laboratory (ANL) and Atomic Energy of Canada Limited (AECL). A successful simulation is performed with an Electrolyte Non Random Two Liquid (ElecNRTL) model of Aspen Plus. The efficiency of the cycle based on three and four step process routes is examined in this thesis. The thermal efficiency of the four step thermochemical process is calculated as 45%, while the three step hybrid thermochemical cycle is 42%, based on the lower heating value (LHV) of hydrogen. Sensitivity analyses are performed to study the effects of various operating parameters on the efficiency, yield, and thermodynamic properties. Possible efficiency improvements are discussed. The results will assist the development of a lab-scale cycle which is currently being conducted at the University of Ontario Institute of Technology (UOIT), in collaboration with its partners.
UOIT

Dissertação de Mestrado Integrado em Engenharia Química apresentada à Faculdade de Ciências e Tecnologia da Universidade de Coimbra
Nos últimos anos, a escassez de recursos fósseis tornou-se uma realidade importante. Aliada aos efeitos ambientais negativos que advêm com a exploração destes recursos, são necessárias alternativas. Nos últimos anos, houve um foco, liderado em grande parte pela Europa em encontrar alternativas aos combustíveis fósseis que sejam verdadeiramente viáveis, especialmente no sector dos transportes. O mercado dos transportes está a crescer rapidamente, muito devido à China e outros países emergentes, o que significa que a procura ligada aos combustíveis para transportes só irá aumentar. De modo a satisfazer esta procura, alternativas ao petróleo são necessárias e os biocombustíveis surgem como um importante recurso. No entanto, ainda existem muitos problemas associados ao processamento das matérias-primas, nomeadamente a biomass, em combustíveis que possam ser usados. Há também o benefício da valorização dos recursos endógenos ao nível económico, social e ambiental. Esta tese pretende descrever a pirólise de cinco tipos de madeira, que podem ser encontradas dentro de Portugal continental. Dois esquemas reaccionais foram testados para todas as amostras e modificações foram feitas de forma a melhor coincidir com resultados experimentais, tal levou ao estudo de um cenário optimizado. Os esquemas retirados da literatura foram usados sem modificações em simulações em Aspen Plus, e apresentaram grandes desvios em relação aos resultados experimentais, com desvios de rendimentos de açúcares e água acima de 15% em erro absoluto. Com as modificações introduzidas, a maior parte dos componentes simulados apresentaram um erro inferior a 2%, com a excepção do char, água e gás, com desvios na ordem dos 3-4%. Tendo a unidade uma capacidade de processamento de 90 ton/dia de biomass, o calor necessário para a pirólise está entre 1.6-1.8MW dependendo do tipo de biomassa, e para todos os casos há excesso de calor (entre 1.75-3MW). Uma análise de sensibilidade permitiu inferir que os esquemas reaccionais usados estão limitados tanto em termos de temperatura como tempo de residência.
In recent years, the scarcity of fossil fuels became an important reality. Allied with the negative environment consequences that come with exploration of these resources, alternatives are needed. In the last years, there has been a focus, driven mostly by Europe into finding truly viable alternatives to fossil fuels, specially in the transportation sector. Rapidly growing transportation markets in China and other developing countries means the demand for transportation fuel will only increase. In order to provide for the ever growing demand the alternative for oil is needed and the importance of biofuels is unquestionable. However there are many problems associated with processing of the feed materials, namely biomass, into usable fuels. Also, there are benefits in the valorization of endogenous resources, at the economical, social and environmental level. The present thesis aims at properly describing pyrolysis of five selected wood samples, that can typically be found within Portugal’s continental borders. Two reaction schemes will be tested for all the samples, and some modifications to better match experimental data, leading to an optimized scenario will also be studied. The schemes retrieved from the literature, used as is in an Aspen Plus simulation environment, present high deviation to experimental data, with water and sugar deviations above 15% in absolute error. When the modification are introduced, most of the components present an absolute error below 2%, with the exception of char, water and gas, which still show deviations in the 3-4% range. With a biomass processing capacity of 90 tons/day, the pyrolysis duty is around 1.6-1.8MW depending on the feedstock, and in all cases there is a heat surplus (between 1.75-3MW). Sensibility analysis shows that the used reaction schemes are limited both in temperature that can be used and residence time.

A research report submitted in partial fulfilment requiremenrs of degree Master of Science tothe School of Chemical and Metallurgical Engineering, Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, South Africa, January 2018
South Africa’s energy sector is vital to the development of its economy. Instability in the form of disruption in supply affects production costs, investments, and social and economic growth. Domestic sources are no longer able to meet the country’s demands. South Africa must find a local alternative fuel source in order to reclaim stability and encourage social and economic development. Biomass is one of the most abundant renewable energy sources, and has great potential as a fuel source. Currently biomass contributes 12% of the world’s energy supply, while in some developing countries it is responsible for up to 50% of the energy supply. South Africa is the highest maize producer on the African continent. Many studies carried out indicated that maize, and its residue contain valuable materials, and has the highest lower heating value in comparison to other agricultural crops. This indicates that maize can be a potential biomass for renewable energy generation in South Africa. A means for energy conversion for biomass, is the process of gasification. Gasification results in gaseous products H2, CO and CO2. Since the process of biomass gasification involves a series of complex chemical reactions involving a number of parameters, which include flow, heat transfer and mass transfer, it is very difficult to study the process of gasification by relying on experimentation only. Numerical simulation was used to provide further insight on this process, and accelerate development and application of maize gasification in a cost effective and efficient manner. The objective of this study was therefore, to verify and evaluate the feasibility of maize gasification and liquid fuels production in South Africa from an economic and energy perspective. The simulation model was developed in Aspen Plus® based on two thermodynamic models specified as Soave – Redlich – Kwong and the Peng Robinson equation of state. All binary parameters required for this simulation were available in Aspen Plus®. The gasification unit was modelled based on a modified Gibbs free energy minimization model. Gasification of maize and downstream processing in the form of Fischer-Tropsch (FT) synthesis and gas to liquids (GTL) processing for liquid fuels production was modelled in Aspen Plus®. Sensitivity analyses were carried out on the process variables: equivalence ratio (ER), steam to biomass ratio (SBR), temperature and pressure, to obtain the optimum gasification conditions. The optimum reactor conditions, which maximized syngas volume and quality was found to be an ER of 0.22 and SBR of 0.2 at a temperature of 611ºC. An increase in pressure was found to have a negative effect; therefore atmospheric conditions of 101.325 kPa were chosen, in order to maximize CO and H2 molar volumes. Based on these conditions the produced syngas consisted of 35% H2, 16% CO, 24% CO2 and 3%CH4. The results obtained from gasification, based on a modified Gibbs free energy model, show a closer agreement with experimental data, than other simulations based on the assumption that equilibrium is reached and no tar is formed. However, these results were still idealistic as it under predicted the formation of CO and CH4. Although tar was accounted for as 5.5% of the total product from the gasifier (Barman et al., 2012), it may have been an insufficient estimation resulting in the discrepancy in CO and CH4. The feasibility of maize as a feed for gasification was examined based on quality of syngas produced in relation to the requirements for FT synthesis. A H2/CO ratio of 2.20 was found, which is within range of 2.1 – 2.56 found to support greater conversions of CO with deactivation of the FT catalyst (Lillebo et al., 2017). The syngas produced from maize was found to have a higher H2/CO ratio than conventional fossil fuel feeds; implying that maize can result in a syngas feed which is both renewable and richer in CO and H2 molar volumes. Liquid fuels generation was modelled based on experimental production distributions obtained from literature for FT synthesis and hydrocracking. The liquid fuel production for 1000 kg/hr maize feed, was found to be 152 kg/hr LPG, 517 kg/hr petrol and 155 kg/hr diesel. The simulation of liquid fuels production via the Fischer-Tropsch synthesis and hydrocracking process showed fair agreement with literature. Where significant deviations were found, they could be reasonably explained and supported. This simulation was found to be a suitable means to predict liquid fuels production from maize gasification and downstream processing. The feasibility of liquid fuels production from maize in South Africa was examined based on the country’s resource capacity to support additional maize generation. It was found that based on 450 000 hectares of underutilized land found in the Homelands, an additional 1.216 billion litre/annum of synthetic fuels in the form of diesel and petrol could be produced. This has the potential to supplement South African liquid fuels demand by 6% using a renewable fuel source. This fuel generation from maize will not impact food security due to the use of underutilized arable land for maize cultivation, or impact water supply as maize does not require irrigation. In addition, fuel generation in this manner supports the Biofuels Industry Strategy (2007) by targeting the use of underutilized land, ensuring minimal impact on food security, and exceeds its primary objective of achieving a 2% blending rate from renewable sources. The economic feasibility of liquid fuels derived from maize was determined based on current economic conditions in 2016. Based on these conditions of 49 $/bbl Brent Crude, 40 $/MT coal and 6.5 $/mmBTU of natural gas at a R/$ exchange rate of R14.06 per U.S. dollar, it was found that coal, natural gas and oil processing are more economically viable feeds for fuel generation relative to maize. However, based on projected market conditions for South Africa, the R/$ exchange rate is expected to weaken further, the coal supply is expected to diminish and supply of natural gas is expected to be a continued issue for South Africa. Based on this, maize should be considered as a feed for fuel generation to reduce the dependency on non-renewable fossil fuel sources. The energy feasibility of liquid fuels produced from maize was only evaluated from a thermal energy perspective. It was found that maize gasification and FT processing requires 0.91 kg steam/kg feed. This 0.91kg of steam accounts for the raw material feed, distillation and heating required for every 1kg of maize processed. It was found that 2.56 kg steam/kg feed was generated from the reactor units. This was assumed to be in the form of 10 bar steam, as in this form it can be sent to steam turbines for electricity generation to assist with overall energy efficiency for this process. In addition, the amount of CO2 (kg/kg feed) produced, was examined for maize processing in comparison to fossil fuel feeds: natural gas and coal. The CO2 production from liquid fuels processing based on a maize feed, was found to be the highest at 0.66 kg/kg feed. However, a coal feed has higher ash and fix carbon content indicating greater solid waste generation in the gasifer. While dry reforming of natural gas is a net consumer of CO2, but had significantly higher steam requirements in order to achieve the same H2/CO ratio as maize. This indicates that although maize results in more CO2/kg feed, it is 88% more energy efficient than dry methane reforming. Additional experimental work on FT processing using syngas derived from maize is recommended. This will assist in further verification of liquid fuels quantity, quality and process energy requirements.
XL2018

Yes
Process simulation of a single-step synthesis of DME based on CO2-enhanced gasification of rice straw was conducted using Aspen PlusTM. The process consists of gasification unit, heat recovery unit, gas purification unit, single-step DME synthesis, and DME separation unit. In the simulation, highly pure DME was produced by the control of CO2 concentration in syngas to a very low level prior to synthesis. A gasification system efficiency of 36.7% and CO2 emission of 1.31 kg/kg of DME were achieved. Bio-DME production based on CO2-enhanced gasification of biomass was found to be more cost-effective as it required 19.6% less biomass than that of DME production based on conventional biomass gasification. The performance and environmental benefits of the proposed process could be further improved by the utilization of unreacted gases and the handling of CO2 generated via incorporating poly-generation concept or carbon storage, which could also potentially improve process economics.
Ningbo Bureau of Science and Technology; Innovation Team Scheme; Major R&D Programme; Provincial Innovation Team on the Commercialisation of SOx and NOx Removal Technologies; University of Nottingham Ningbo China

A dissertation submitted to the faculty of Engineering and the Built Environment, University of the Witwatersrand, in fulfillment of the requirements for the degree of Master of Science in Engineering. 21 November 2016
In this work a comprehensive exergy analysis and heat integration study was carried out on a coal based oxy-combustion power plant simulated using ASPEN plus. This is an extension on the work of Fu and Gundersen (2013). Several of the assumptions made in their work have been relaxed here. Their impact was found to be negligible with the results here matching closely with those in the original work. The thermal efficiency penalty was found to be 9.24% whilst that in the original work was 9.4%. The theoretical minimum efficiency penalty was determined to be 3% whilst that in the original work was 3.4%. Integrating the compression processes and the steam cycle was determined to have the potential to increase net thermal efficiency by 0.679%. This was close to the 0.72% potential reported in the original work for the same action.
MT2017

Yes
The biomass gasification process is widely accepted as a popular technology to produce fuel for the application in gas turbines and Organic Rankine Cycle (ORC). Chemical reactions of this process can be separated into three reaction zones: pyrolysis, combustion, and reduction. In this study, sensitivity analysis with respect to three input parameters (gasification temperature, equivalence ratio, and steam-to-biomass ratio) has been carried out to achieve energy self-sufficient conditions in a steam gasification process under the criteria that the carbon conversion efficiency must be more than 70%, and carbon dioxide gas is lower than 20%. Simulation models of the steam gasification process have been carried out by ASPEN Plus and validated with both experimental data and simulation results from Nikoo & Mahinpey (2008). Gasification temperature of 911 °C, equivalence ratio of 0.18, and a steam-to-biomass ratio of 1.78, are considered as an optimal operation point to achieve energy self-sufficient condition. This operating point gives the maximum of carbon conversion efficiency at 91.03%, and carbon dioxide gas at 15.18 volumetric percentages. In this study, life cycle assessment (LCA) is included to compare the environmental performance of conventional and energy self-sufficient gasification for steam biomass gasification.
Financing of this research was supported by the Thailand Research Fund (TRF) under Grant Number PHD57I0054 and the Institutional Research Grant by the Thailand Research Fund (TRF) under Grant Number IRG 5780014 and Chulalongkorn University, Contact No. RES_57_411_21_076.