Dissertations / Theses on the topic 'ASPEN-Plus'

This thesis project is focusing on the modeling, optimization and control analysis of a debutanizer column using Aspen PLUS and Aspen Dynamics. A complex mixture of hydrocarbons contained a different range of hydrogen and carbon from C2 until nC8 was fed into the debutanizer column for the separation process. There are two products coming out from this distillation column; the light-end hydrocarbons (C2-C4) and the heavier-end hydrocarbons (C5+). The C2-C4 became the desired product for debutanizer column which required to be separated from the mixed hydrocarbons. This C2-C4 was removed from distillate stream as an overhead product. Meanwhile, the C5+ was removed from the bottoms stream as a bottoms product. The target of this project was to recover 90% of butane (C4) and maximum 5 mol% of pentane (C5) composition in the distillate stream. This target was achieved at the end of the project by obtaining approximately 91.1% of C4 recovery and 4.039 mol% of C5 in the distillate stream. Therefore, it concluded the recovery of C5 in the bottoms stream was 90.3%. The debutanizer model was firstly constructed in the Aspen PLUS for steady-state simulation which relied on several specifications of the column and the criteria of the process. The simulation of this separation process was designed using rigorous distillation column simulator, RadFrac. A comparison of physical property methods between Peng-Robinson and RK-Soave were investigated by considering the same theoretical stages in each configuration. Then, the final type of property model was selected depending on the lowest offset from industrial data. A sensitivity analysis was performed to simulate the column within a range of the parameter, and an optimization problem was formulated to be solved. The steady-state flowsheet generated in Aspen PLUS was exported into Aspen Dynamics to simulate the column in dynamic simulation. The debutanizer system has multiple input variables to control the multiple output variables. Therefore, the relative gain array (RGA) analysis was calculated based on the steady-state gain obtained from open loop transfer functions to find the best pairing of input-output. The conventional Proportional-Integral (PI) and cascade control were implemented into the debutanizer column and both control required to be tuned. Therefore, a relay auto-tuning in Aspen Dynamics was used to determine the ultimate period (Pu) and ultimate gain (KCU) of each process. Then, the controller parameters could be calculated using Ziegler-Nichols method. The control strategy was carried out to observe the process response towards changes of set-point and to analyze the relationships between the process variables (PV) and manipulated variables (MV). The disturbance rejection was performed to determine the success of established control scheme. At the end of the project, multiple comparisons were made between the results obtained from Aspen PLUS and Aspen Dynamics with the literature papers. Overall, all thesis objectives were completed, and the purpose of the debutanizer column to be simulated in Aspen PLUS and Aspen Dynamics were successful.

Orientador: Maria Regina Wolf Maciel<br>Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica<br>Made available in DSpace on 2018-08-01T10:10:37Z (GMT). No. of bitstreams: 1 Torres_ArmandoAntoniodeOliveira_M.pdf: 3727476 bytes, checksum: fd50582b75f3a0a86a9bcd1a8428aa68 (MD5) Previous issue date: 2001<br>Resumo: O Processo Bayer é definido como uma tecnologia para a produção de óxido de alumínio (Ah03), principal matéria prima para a produção de Alumínio. Este processo transforma o minério de bauxita em alumina Ah03, utilizando soda cáustica e vapor gerado por caldeiras. Os sub processos que compõem o processo Bayer são a Moagem, Digestão, Filtração, Troca Térmica, Precipitação, Calcinação e Evaporação. Utilizando os dados da Refinaria de Poços de Caldas e trabalhando no Laboratório de Desenvolvimento de Processos de Separação da Faculdade de Engenharia Química da Unicamp, foi desenvolvido um método que utiliza os modelos existentes no software Aspen Plus para compor o "Modelo do Processo Bayer".O principal objetivo deste trabalho foi inter-relacionar os modelos do Aspen Plus para representar a Refinaria de Poços de Caldas, simulando o balanço de massa e energia do processo Bayer. A simulação foi conduzi da utilizando o módulo do simulador para sistemas eletrolíticos, considerando o estado dos componentes em seu modo verdadeiro, para melhor representar a não idealidade da solução. O licor do processo Bayer é uma solução eletrolítica, em que a água é o solvente e os demais componentes da mistura, NaOH, NaAlOz, NazCO3 estão completamente dissociados em íons como Na+, AlOz-, CO3-z, e OH-. As operações unitárias utilizadas do software para construir o "Modelo do Processo Bayer" foram o reator estequiométrico, tanques de "flash", lavadores simples, decantadores de contra corrente, misturadores, aquecedores e condensadores. O processo Bayer é controlado através do monitoramento das concentrações alcalina (TA), cáustica (TC) na unidade de equivalente g NazCO3 por litro de licor, como também a concentração de alumina em g AlzO3 por litro de licor. Foi necessário desenvolver uma metodologia que transformasse estas concentrações para expressões na base em massa para os compostos NaOH, NaAlOz, NazCO3 e água. A equação de densidade do Aspen Plus apresentou um desvio de 15% quando tentou-se obter os volumes e massas da solução. Foi necessária a utilização de uma outra equação de densidade (Equação de Russel) para desenvolver o método de transformação das concentrações de solução em massa. Comparando-se este método com dados analíticos, encontrou-se desvios da ordem de 1 %, demonstrando grande precisão do método. A entrada de dados para as simulações foram provenientes de amostras e análises químicas do licor e medidas de fluxo, temperatura e pressão do processo produtivo. Com os resultados da simulação do "Modelo do Processo Bayer", as massas dos íons Na+, AL02-, C03-2, e OH- são obtidas, as quais são transformadas em concentrações nas bases TA, TC e AhO3, para que seja possível a comparação entre os resultados do modelo e os dados analíticos de cada sub processo. Os desvios entre os resultados dos modelos de cada sub processo e as concentrações de planta estiveram entre O e 3 %. F oram utilizados fatores de ajuste para representar o sub processo da digestão e a evaporação natural dos tanques de processo para aumentar a precisão do modelo. O "Modelo do Processo Bayer" apresentou baixos desvios da realidade quando foram comparadas com as concentrações da solução cáustica da planta e as geradas pelo modelo. Foi observado o grande potencial de utilização nas seguintes atividades: Planejamento operacional e estimativa do custo de produção da alumina de acordo com o consumo de soda, bauxita e energia. Controle de volume da planta. Predizer as concentrações cáusticas do licor; Diferenças e perdas de energia em aquecedores; Identificação de anonnalidades no processo<br>Abstract: (AlzO3), main raw material to produce Aluminum. This process transforms Bauxite ore in a white sand alumina (AlzO3), using Caustic Soda and Steam from the Boilers. The sub processes that represent a Bayer Refinery are Grinding, Digestion, Filtration, Heat Exchange, Precipitation, Ca1cination and Evaporation. Using the Poços de Caldas Refinery data, and working at the Separation Process Development Laboratory at Campinas State University, a method to link the models in Aspen Plus software, to build up the Bayer process was developed. The main objective of this work was to interrelate the models from the Aspen Plus to represent the Poços de Caldas Refinery, to simulate the Energy and Mass Balances from the Bayer Process. Simulation for Electrolyte Systems were performed, with true components and to represent the non-ideality ofthe liquid solution, the NRTL thermodynamic model was used to get the activity coefficients in order to calculate the vapor-liquid phase equilibria. The Bayer liquor is an electrolyte solution, in which water is the solvent and the components from the mixture, NaOH, NaAlO2, Na2CO3 are completely dissociated in ions as Na+, AlO2-, CO3-Z and OH-. The unit operations used from the software to build up the Bayer process are: Stoichometric Reactor, Flash Tank, Single Wash, Counter Current Decanter, Mixers, Heaters and Condensers. The Bayer process is controlled by following the alkaline, caustic and alumina concentrations in equivalent unit (g Na2CO3 per liquor liter). A methodology to transform this concentration expression in mass of NaOH, NaAlOz, Na2CO3 and water was necessary to be developed. The density equation from the Aspen Plus gave 15% of error when it was tried to calculate the volumes or the masses. Another equation (Russell equation) was, then, used to develop the method to transform the concentration number in mass. Comparing with analytical data, the error were about 1 %, giving a good accuracy to the translated method. Samples and chemical analyses, flows, temperature and pressure measurements are the inputs for the model from the planto The outputs from the "Bayer Model" in Na+, AIO2-, CO3-and OR mass, were transformed in TA, TC and AhO3 concentrations (Alkaline, Caustic and Alumina concentration) to compare with the results of the analytical plant that were collected in the outlets from each sub processo Each sub processes was runned and the outputs plant concentrations were compared with the results from Aspen giving deviations between O and 3%. Fitting factors in the reactor to represent the digestors were used. The natural evaporation that occurs in the tanks was necessary to be considered in the model to increase its accuracy. The Bayer Model developed can be used to: Control the plant volume. Predict liquor concentration and find ilegal dilution in the process. Carry out an operating plan and to estimate the alumina cash cost according to the consumption of Soda, Bauxite and Energy Proceed with mass and energy balances and lost in the heaters. So, using the models from Aspen Plus for Electrolyte System, it is possible to build up a "Bayer Process Model" to represent a Plant with deviation between O to 3%. With this accuracy, the model can predict the energy and mass balances and the solution concentrations from the plant liquor. The density equation from Russell is necessary to be used to get the accuracy commented to translate the liquor concentration (TA, TC and AhO3) to the NaOH, NaAlO2, Na2CO3 and Water<br>Mestrado<br>Desenvolvimento de Processos Químicos<br>Mestre em Engenharia Química

Syftet med den här studien är att göra en teknoekonomisk utvärdering av processer för förvätskning av CO2 med hjälp av Aspen Plus. Ett flertal förvätskningsprocesser från tidigare studier jämfördes och från dessa valdes två förvätskningsprocesser ut för fortsatta studier och simuleringar. Dessa två förvätskningsprocesser var ett internt kylt förvätskningssystem och ett externt kylt förvätskningssystem av Øi et al., Energy Procedia 86 (2016) 500-510, som kallats system A, samt av Seo et al., International Journal of Greenhouse Gas Control 35 (2015) 1-12 kallat system B. Dessa två olika processer simulerades för teknisk analys med hjälp av Aspen Plus. Aspen Economical Analyzer (AEA) användes för att göra den ekonomiska analysen. I dessa simuleringar användes ett massflöde på 45 ton/h inkluderat vatteninnehåll, i jämförelse med tidigare studier med högre massflöden runt 100 ton/h. Elektricitet-och kylbehovet undersöktes i ett flertal olika fall med varierande kyltemperatur mellan kompressorerna. Två fall med integrering av fjärrvärme samt två fall med en värmepump undersöktes också med varierande återgående temperatur på fjärrvärmevattnet. Detta gjordes för att undersöka hur mycket värme som kan tillvaratas från förvätskningsprocessen. Vidare bestämdes även investeringskostnader samt driftskostnader med hjälp av AEA. Från detta bestämdes även den årliga kostnaden av kapitalet, CAPEX, och kostnaden att förvätska CO2 räknades ut i form av €/ton.  Resultaten visade att integrering av fjärrvärme samt värmepumpar är användbart för att tillvarata på så mycket värme som möjligt från förvätskningssystemen. I de fall med en värmepump samt en återgående temperatur på 47°C i fjärrvärmenätet hade ett COP på 3.07 samt 3.15 för system A samt system B vardera. Kostanden att förvätska CO2 var 17.42 €/ton för system A samt 17.75 €/ton för system B utan använding av en värmepump samt en återgående temperatur på 47°C i fjärrvärmenätet. Vid integrering av en värmepump gick kostnaden av förvätskning upp till 20.85 €/ton för system A samt 21.69 €/ton för system B. Kostnaden av förvätskning dominerades av driftskostnader med kostnaden av kapitalet har en mindre påverkan. Utnyttjandegraden har även en stor påverkan på kostanden av förvätskning, då lägre kapaciteter visade sig leda till markant högre förvätskningskostnader. När intäkterna från fjärrvärmeproduktionen adderades till kostnadskalkylen, minskade kostnaden av förvätskning, speciellt för de system med en värmepump, där priset minskade till 10.26 €/ton för system A eller 10.98 €/ton för system B. I linje med tidigare studier pekar även dessa resultat på att det ekonomiska optimumet sammanfaller med energioptimum. Resultaten visade även att system A, det internt kylda systemet, hade den lägsta förvätskningskostanden och minsta elektricitetsförbrukningen med och utan värmepump, och därför är system A optimalt för småskalig CO2 förvätskning.<br>The aim of this study is to do a technoeconomical analysis on CO2 liquefaction systems using Aspen Plus. Several liquefaction systems from previous studies were compared, and from these, two liquefaction systems were chosen for further studies and simulations. These liquefaction systems were namely an internal liquefaction system and an external liquefaction system by Øi et al., Energy Procedia 86 (2016) 500-510, called system A and Seo et al., International Journal of Greenhouse Gas Control 35 (2015) 1-12, called system B. These systems were simulated for technical analysis using Aspen Plus, and Aspen Economical Analyzer (AEA) was used for economical studies. A small-scale liquefaction system was studied with a mass flow rate of 45 tonne/h including the water content, as compared to other studies with higher mass flow rates of around 100 tonne/h. The electricity demand and cooling demand were studied in several cases of interstage cooling between compressors. Furthermore, two cases of district heating as well as two cases of heat pumps were studied with varying return temperatures of the district heating water. This was done to study how much heat could be recovered from the liquefaction process. Furthermore, the capital expenses as well as the operating expenses were also determined using AEA. From this, the annual CAPEX and the cost of CO2 was calculated in terms of €/tonne CO2.  The results showed that district heating and heat pumps can be useful to recover heat from the liquefaction processes. The simulations that included a heat pump and assumed a return temperature of 47°C had a COP of 3.07 and 3.15 for system A and B respectively. The determined cost of production was 17.42 €/tonne for system A and 17.75 €/tonne for system B when not using a heat pump and a return temperature of 47°C in the district heating grid. However, when adding a heat pump the total production cost (TPC) increased to 20.85 €/tonne for system A, and 21.69 €/tonne for system B. It was also shown that the TPC is highly dominated by the operating expenses while the total capital investment has a smaller impact on the TPC. The capacity is also important for the TPC as lower capacities was shown to lead to significantly increased production costs. When taking the revenue streams from district heating into account the TPC was decreased, in particular for the systems including the heat pumps, where the TPC for system A was 10.26 €/tonne while for system B it was 10.98 €/tonne. In accordance with previous studies it was shown that the economical optimum is closely related to the energy optimum. It was concluded that as system A, the internal liquefaction system, had the lowest TPC and electricity input with and without the heat pump and thus it is the optimal configuration for small-scale CO2 liquefaction.

Gasification of petroleum coke (Petcoke) has emerged in the last decades as one of the attractive options and is gaining more attention to convert petcoke and oil residue to synthesis gas (Syngas). Syngas consists mainly of hydrogen (H2), carbon monoxide (CO), some other gases, and impurities. In this study, a simulation of Tuscaloosa petcoke, typical gulf coast refineries petcoke, gasification was developed using ASPEN PLUS software. Sensitivity analysis of the simulated model was performed to study the variation in operation conditions of the gasifier such as temperature, pressure, oxygen flow rate, and steam flow rate. The approach correlates the behavior of these parameters with the syngas yield (i.e., H2, CO, CO2, H2O, CH4, and H2S). Consequently, the desired syngas yield can be obtained by manipulating the gasifier parameters. Implementing optimization calculation shows that up to (81 %) of the gasifier cold gas efficiency (Based on LHV) can be achieved for the developed model. Therefore, Tuscaloosa petcoke gasification under the aforementioned parameters is feasible and can be commercialized. This leads to more utilization of the bottom of oil barrel by upgrading it to more valuable gases with less environmental impacts.

This project modelled a thermal liquefaction industrial facility for biofuel production from sugarcane bagasse using the process modelling software ASPEN Plus. Techno-economic models of liquefaction, pyrolysis and gasification processes were completed to assess the comparative feasibility of these thermochemical biofuel production processes. Model liquefaction biocrudes, were developed in ASPEN Plus using simulated distillation data and this method's utility in modelling biocrudes was validated.

The aim of this research was to produce an integrated modelling platform in which an anaerobic digester could be linked to the other unit operations which serve it, both in maintaining the physical-chemical conditions in the digester and in transforming the digestion products to useful fuel and nutrient sources. Within these system boundaries an accurate mass and energy balance could be determined and further optimised, particularly where the desired energy products are a mix of heat, power, and biomethane. The anaerobic digestion of food waste was choosen as the subject of the research because of its growing popularity and the availability of validation data. Like many other organic substrates, food waste is potentially a good source of renewable energy in the form of biogas through anaerobic digestion. A number of experimental studies have, however, reported difficulties in the digestion of this material which may limit the applicability of the process. These arise from the complexity of the biochemical processes and the interaction between the microbial groups that make up the anaerobic community. When using food waste there is a tendency to accumulate intermediate volatile fatty acid products, and in particular propionic acid, which eventually causes the pH to drop and the digester to fail. Two factors are important in understanding and explaining the changes in the biochemical process that leads to this condition. The first is due to the differential in sensitivity to free ammonia of the two biochemical pathways that lead to methane formation. The acetoclastic methanogenic route is inhibited at a lower concentration than the hydrogenotrophic route, and methane formation therefore occurs almost exclusively via acetate oxidation to CO2 and H2 at high free ammonia concentrations. The accumulation of propionic acid is thought to be because formate, a product of its degradation, cannot be converted to CO2 and H2 as the necessary trace elements to build a formate dehydrogenase enzyme complex are missing. The Anaerobic Digestion Model No. 1 (ADM1) was modified to reflect ammonia inhibition of acertoclastic methanogenesis and an acetate oxidation pathway was added. A further modification was included which allowed a 'metabolic switch' to operate in the model based on the availability of key trace elements. This operated through the H2 feedback inhibition route rather than creating a new set of equations to consider formate oxidation in its own right: the end result is, however, identical in modelling terms. With these two modifications ADM1 could simulate experimental observations from food waste digesters where the total ammoniacal nitrogen(TAN) concentration exceeded 4 gN l-1. Under these conditions acetate accumulation is first seen, followed by proprionate accumulation, but with the subsequent decrease in acetate until a critical pH is reached. The ADM1 model was implemented in MATLAB with these modifications incorporated. The second part of the research developed an energy model which linked ADM1 to the mechanical processes for biogas upgrading, Combined Heat and Power (CHP)production, and the digester mixing system. The energy model components were developed in the framework of the Aspen Plus modelling platform, with sub-units for processes not available in the standard Aspen Package being developed in Fortran, MS Excel or using the Aspen Simulation Workbook (ASW). This integration of the process components allows accurate sizing of the CHP and direct heating units required for an anaerobic digestion plant designed for fuel grade methane production. Based on the established model and its sub-modules, a number of case studies were developed. To this end the modified ADM1 was applied to mesophilic digestion of Sugar Beet Pulp to observe how the modified ADM1 responded to different substrate types. Secondly, to assess the capability of adding further mechanical processes the model was used to integrate and optimise single stage biogas upgrading. Finally, the digestion of food waste in the municipal solid waste stream of urban areas in Vietnam was considered.

In practice, distillation may be carried out by either of two methods. The first method is based on the production of vapor by boiling the liquid mixture to be separated and condensing the vapour without allowing any liquid to return to the still. Then, there is no reflux. The second method is based upon the return of part of the condensate to the still under such conditions that this returning liquid is brought into the intimate contact with the vapours on their way to the condenser. Either of these two methods may be conducted as a continuous or as a batch process, but the study of dynamics and control of the process is one of most important part of each process. Distillation is one of the commonly used separation technique in the chemical industries. The separation is based on differences in “volatilities” (tendencies to vaporize) among various chemical components. In a distillation column the more volatile, or lighter, components are removed from the top of the column, and the less volatile, or heavier, components are removed from the lower part of the column. Further Aspen Plus makes it easy to build and run the process simulation model by providing with a comprehensive system of the online process modelling. Process simulation allows one to predict the behaviour of a process by using basic engineering relationships, such as mass and energy balances, and phase and chemical equilibrium. Process simulation enables one to run many cases, conduct „what if‟ analysis and perform sensitivity analysis and optimization runs. With simulation one can design better plants and increase the profitability of the existing plants. Process simulation is helpful throughout the entire life of a process, from research and development through process design to production. This thesis studies the dynamics and control of distillation columns using Aspen Plus. In this thesis, simulation studies of the distillation column are presented. Steady-state simulations are being performed using Aspen Plus followed by Aspen Dynamic simulation. In the steady state simulation, it was tried to see the effect of changing the flow rate of the extractive distillation. And finding the optimum flow rate in the distillation column. Controllers are then implemented for controlling sump level, reflux level and feed flow rate. Furthermore, two strategies were used for controlling the purity of distillate product controlling the distillation column tray temperature where the maximum change of temperature is observed due to reboiler heat change and the purity of the product by using composition controller. The case study was an example taken from Aspen Plus (version 8.4v). In the example, there are two main streams enters the distillation column and phenol will be the stream one, and methyl cyclone hexane (MCH) and toluene mixer will enter the distillation column as the second stream. MCH has been distilled from the top of the column and the phenol and toluene the bottom product. With the latest Aspen Plus and Aspen Dynamics version V10 with operating under Windows 10, because of that, we will come across few compatibility issues in Aspen Dynamics mainly when it comes to MATLAB. Moreover, due to incompatibility MATLAB and Simulink were not tested for this process. In this study, Methyl Cyclo Hexane (MCH) been separated from Toluene by using Phenol as the third component in an extractive distillation column. And in Aspen Dynamics new controllers been developed to control the product Methyl Cyclo Hexane (MCH) purity by making adjusting the flow rate level of the Phenol. DMC controllers were tried to implement in the process to replaces the PI controller but fail attempt. All the PI controllers have been auto-tuned in Aspen Dynamics using it tool of the faceplates. Which given the best possible controller parameters to for the process. Therefore, all the controller’s other was able to reach its set-point expect the composition controller. The controllers were helping to achieve the maximum purity of the distillate stream. All the obtained results have been discussed and the Important guidelines been outlined and explained in the overall simulation. Most of the objective been achieved in this thesis.

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.<br>Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2012.

The present work investigates further development of a small-scale fixed bed batch operating gasification pilot system intended to be used as a waste-to-energy process to reduce littering of PET-bottles on Pemba Island in Tanzania. By developing a simplified gasification model and identifying the most important parameters to obtain a syngas with a lower heating value suitable for combustion and maximizing the overall efficiency and cold gas efficiency. By a literature study the most important parameters were identified along with how the methodology for developing the model and selection of modelling software. The model was developed as an equilibrium-based model in Aspen Plus representing the pilot system, the most important parameters was identified as equivalence ratio and temperature. Multiple scenarios, regarding sensitivity analysis of these parameters was conducted to determine how the outcome of the process was affected. The model was validated against a reference study and was proven to be accurate with small variations. High content of methane and carbon monoxide promoted the highest lower heating value which was at an equivalence ratio of 0.25 and a temperature of 450°C, which also indicated the highest overall efficiency. Increasing the temperature favoured the carbon monoxide content and the cold gas efficiency but indicated a decrease in lower heating value and overall efficiency. It was concluded that the optimal operational conditions were at an equivalence ratio at 0.25 and a temperature at 450°C. At these conditions, the formation of by-products from the gasification is higher than at higher equivalence ratios and temperature which needs to be further investigated through experimental work. It was also concluded that the system could benefit to operate in a semi- batch configuration with a higher equivalence ratio to utilize the excess heat from the process.

Master of Science<br>Department of Chemical Engineering<br>Larry Erickson<br>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.

I den här rapporten utvärderas det nya konceptet Power &amp; Biomass to Liquid (PBtL). PBtL är ett alternativ till den tidigare och mer etablerade Biomass to Liquid (BtL) processen. Med PBtL förbättras utbytet av kol jämfört med BtL genom att elektricitet läggs till i processen. Elektriciteten används för att producera H2, som används för att höja H2/CO förhållandet istället för att använda WGS som i vanlig BtL process. Rapporten är en del i ett större PBtL projekt som bedrivits vid Institutt for kjemisk prosessteknologi vid NTNU och på SINTEF. Utvärderingen utfördes genom flera simuleringar av lågtemperaturs Fischer-Tropsch reaktorer i simuleringsprogrammet Aspen Plus. Omvandling och katalytiska reaktorer utvecklades och togs fram i programmet. Produktfördelningen i omvandlingsreaktorn modellerades med ASF distribution theory tillsammans med en metod för sammanslagning av högre kolväten. Fördelningen av paraffiner, olefiner och oxygenater baserades på experimentella resultat från Shafer et al. som studerade en slurryreaktor under liknande förhållanden. Den kinetiska reaktorn modellerades med en variant av ASF fördelningsteori kallad ”consorted vinylene mechanism” från Rytter och Holmen. Reaktorerna adderades till förgasningsprocess, som utvecklats tidigare av PBtL gruppen, I förgasningsprocessen förgasas biomassa till syntesgas, dvs H2 och CO. För att möjliggöra en utvärdering av det efterföljande steget med separering av vax, mellandestillat och lättare kolväten så antogs en väl fungerande separation av Fischer-Tropsch produkterna. En enklare separation av med flash förångning gjordes också, dels för fortsättningen av PBtL processen och för att kunna studera tailgasrecirkulering. Ett mindre bidrag var studier av en torkningsprocess för biomassa innan inloppet till förgasningsprocessen. PBtL konceptet diskuterades även ur ett praktiskt perspektiv.  Resultaten visar att vid driftbetingelser på 210 °C, 25 bar och H2/CO = 1,95 så gav omvandlingsreaktorn en kolselektivitet för CH4 respektive C5+ på 14,77 respektive 75,40 mol% C. Högre temperatur, tryck och H2/CO förhållande i reaktorn resulterar i en högre kolselektivitet mot lägre kolväten. Vid samma driftbetingelser gav den katalysreaktorn en kolselektivitet för CH4 respektive C5+ på 7,612 respektive 86,00 mol% C. Resultaten visar att C8-C16 produktionen var högre än C17+ med avseende på molflöde men lägre beträffande massflöde för katalysreaktorn. Generellt så ökar kolselektiviteten med ökande kolnummer till ett maximum runt 13 för att sedan minska.<br>In this report, the new Power &amp; Biomass to Liquid (PBtL) concept was evaluated. The PBtL concept is a new alternative to the more well-established Biomass to Liquid (BtL) concept where electricity is added to the process. The main purpose for developing the PBtL is that the BtL process exhibits poor carbon efficiency compared to the PBtL process. The electricity here is used to produce H2 in electrolysis. The report is part of a larger PBtL project pursued for several years at the Department of Chemical Engineering at NTNU and SINTEF. The evaluation was done by simulating different types of low temperature Fischer-Tropsch reactors in simulation software Aspen Plus. A conversion reactor and a kinetic reactor was developed. A conversion reactor based on the result from the kinetic reactor was also developed.  The conversion-based reactor was modeled with the ASF distribution theory which describes the distribution of products formed in Fischer-Tropsch synthesis along with a method of lumping higher hydrocarbons. The distribution between paraffins, olefins and oxygenates was based on experimental data from Shafer et al. with similar operating condition with a Slurry reactor. The kinetic-based reactor was modeled with ASF distribution theory with a consorted vinylene mechanism previously described in Rytter and Holmen. The reactors were added to a process for which the biomass gasification section had previously been developed by the PBtL group. The Fischer-Tropsch products were as well separated in order to evaluate the subsequent step of separation of waxes, middle distillate and lighter hydrocarbons. This enabled the option of recycling of tail gas to the Fischer-Tropsch reactor to be evaluated. A smaller contribution included addition of a biomass dryer prior the biomass gasification section. The PBtL concept is also shortly discussed from a practical point-of-view.  It was found that for the operating condition of 210 °C, 25 bar and H2/CO = 1.95 for the conversion-based reactor yielded a carbon selectivity towards CH4 and C5+ of 14.77 and 75.40 mol C% respectively. For the same operating condition, the kinetic-based reactor yield a carbon selectivity towards CH4 and C5+ of 7.612 and 86.00 mol C% respectively. It could be seen from the conversion-based reactor that elevating temperature, pressure and H2/CO (to a certain extent) results in higher carbon selectivity towards lower hydrocarbons. From the product separation with the kinetic reactor, it was observed that C8-C16 production was higher than the C17+ production in terms of mole flow but lower in terms of mass flow. For both models, carbon selectivity increases with carbon number and peaks around carbon number 13 and then starts to decrease.

The modern concept of “biorefinery” is dominantly based on chemical pulp mills to create more value than cellulose pulp fibres, and energy from the dissolved lignins and hemicelluloses. This concept is characterized by the conversion of biomass into various bio-based products. It includes thermochemical processes such as gasification and fast pyrolysis. In thermo-mechanical pulp (TMP) mills, the feedstock available to the gasification-based biorefinery is significant, including logging residues, bark, fibre material rejects, bio-sludges and other available fuels such as peat, recycled wood and paper products. On the other hand, mechanical pulping processes consume a great amount of electricity, which may account for up to 40% of the total pulp production cost. The huge amount of purchased electricity can be compensated for by self-production of electricity from gasification, or the involved cost can be compensated for by extra revenue from bio-transport fuel production. This work is to study co-production of bio-automotive fuels, bio-power, and steam via gasification of the waste biomass streams in the context of the mechanical pulp industry. Ethanol and substitute natural gas (SNG) are chosen to be the bio-transport fuels in the study. The production processes of biomass-to-ethanol, SNG, together with heat and power, are simulated with Aspen Plus. Based on the model, the techno-economic analysis is made to evaluate the profitability of bio-transport fuel production when the process is integrated into a TMP mill.The mathematical modelling starts from biomass gasification. Dual fluidized bed gasifier (DFBG) is chosen for syngas production. From the model, the yield and composition of the syngas and the contents of tar and char can be calculated. The model has been evaluated against the experimental results measured on a 150 KWth Mid Sweden University (MIUN) DFBG. As a reasonable result, the tar content in the syngas decreases with the gasification temperature and the steam to biomass (S/B) ratio. The biomass moisture content is a key parameter for a DFBG to be operated and maintained at a high gasification temperature. The model suggests that it is difficult to keep the gasification temperature above 850 ℃ when the biomass moisture content is higher than 15.0 wt.%. Thus, a certain amount of biomass or product gas needs to be added in the combustor to provide sufficient heat for biomass devolatilization and steam reforming.For ethanol production, a stand-alone thermo-chemical process is designed and simulated. The techno-economic assessment is made in terms of ethanol yield, synthesis selectivity, carbon and CO conversion efficiencies, and ethanol production cost. The calculated results show that major contributions to the production cost are from biomass feedstock and syngas cleaning. A biomass-to-ethanol plant should be built over 200 MW.In TMP mills, wood and biomass residues are commonly utilized for electricity and steam production through an associated CHP plant. This CHP plant is here designed to be replaced by a biomass-integrated gasification combined cycle (BIGCC) plant or a biomass-to-SNG (BtSNG) plant including an associated heat &amp; power centre. Implementing BIGCC/BtSNG in a mechanical pulp production line might improve the profitability of a TMP mill and also help to commercialize the BIGCC/BtSNG technologies by taking into account of some key issues such as, biomass availability, heat utilization etc.. In this work, the mathematical models of TMP+BIGCC and TMP+BtSNG are respectively built up to study three cases: 1) scaling of the TMP+BtSNG mill (or adding more forest biomass logging residues in the gasifier for TMP+BIGCC); 2) adding the reject fibres in the gasifier; 3) decreasing the TMP SEC by up to 50%.The profitability from the TMP+BtSNG mill is analyzed in comparison with the TMP+BIGCC mill. As a major conclusion, the scale of the TMP+BIGCC/BtSNG mill, the prices of electricity and SNG are three strong factors for the implementation of BIGCC/BtSNG in a TMP mill. A BtSNG plant associated to a TMP mill should be built in a scale above 100 MW in biomass thermal input. Comparing to the case of TMP+BIGCC, the NR and IRR of TMP+BtSNG are much lower. Political instruments to support commercialization of bio-transport fuel are necessary.<br>Gasification-based Biorefinery for Mechanical Pulp Mills

Orientador: Antonio José de Almeida Meirelles<br>Texto em português e inglês<br>Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos<br>Made available in DSpace on 2018-08-21T10:31:20Z (GMT). No. of bitstreams: 1 Batista_FabioRodolfoMiguel_D.pdf: 2503364 bytes, checksum: 981f60d79f8a7a65e7ab2c5b944ab1d7 (MD5) Previous issue date: 2012<br>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<br>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<br>Doutorado<br>Engenharia de Alimentos<br>Doutor em Engenharia de Alimentos

The energy intensive distillation process has become a widely discussed topic as industry attempts to minimise energy consumption. The implementation of Model Predictive Control (MPC) can aid in the reduction of plant energy consumption. However, the leading chemical and petroleum software packages Aspen Plus and Aspen HYSYS do not currently support MPC. This project successfully integrated both MATLAB and LabVIEW with Aspen Plus Dynamics (APD), which enables the implementation of MPC schemes. This integration was established using Microsoft’s ActiveX Technology. In order to implement MPC from within MATLAB and LabVIEW, their respective MPC toolboxes were explored; these toolboxes possess several major flaws in their functionality. In particular, neither have the ability to perform RGA analysis or determine the model of the plant through data-driven modelling. To overcome these drawbacks a MATLAB script was developed which determines the model of the plant from automatic step tests in Simulink. Once the communication was established, and toolboxes documented, a high-fidelity distillation column was constructed in Aspen Plus before being exported to APD. This plant model was developed as a reference to compare the effectiveness of the PI and MPC control schemes, employing the Integral of Time-Weighted Absolute Error (ITAE) performance criterion. MPC outperformed the PI control schemes in all but one scenario. On average the ITAE values were 1000% lower for MPC, due to its ability to quickly track the set point and avoid overshoot. Further research has been highlighted on a number of toolbox features and dynamic communication options. Importantly, the use of the integrated software packages can provide a number of benefits for students and personnel. By developing a dynamic template it will be possible to implement these ideas into university, laboratory and workplace training. This could increase confidence in predictive control schemes, operator plant knowledge and reduce unsafe plant operation.

Orientadores: Maria Regina Wolf Maciel, Betânia Hoss Lunelli<br>Tese (doutorado) ¿ Universidade Estadual de Campinas, Faculdade de Engenharia Química<br>Made available in DSpace on 2018-08-26T13:48:19Z (GMT). No. of bitstreams: 1 Ardila_YuranyCamacho_D.pdf: 7705979 bytes, checksum: 19a2840a168991456944a44d857667ee (MD5) Previous issue date: 2015<br>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<br>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<br>Doutorado<br>Desenvolvimento de Processos Químicos<br>Doutora em Engenharia Quimica

This case study investigates the co-simulation of an extractive distillation column using Aspen Dynamics together with MATLAB Simulink toolbox. This extractive distillation column separates Methyl Cyclo Hexane (MCH) from Toluene by using input Phenol as a third component (entractant) to move the ternary system beyond the azeotropic point. The study started with testing the steady state model of the process in Aspen Plus; then continued with importing and testing the process dynamic model in both manual and automatic modes using Aspen Dynamics. Finally, the process model in Aspen Dynamics was connected to the built-in controllers in Simulink then the co-simulation of the controlled process was performed using Aspen Dynamics together with the MATLAB Simulink toolbox. The case study was an example taken from Aspen Dynamics version 8.4v. With the newest version of Aspen Dynamics and Simulink version 8.4 operating platform Windows 7, it is required to install the 32 bit MATLAB to address compatibility issues between Aspen Dynamics and MATLAB. The same control system design including four conventional controllers was implemented by Aspen Tech in two different software package structures: in Aspen Dynamics stand-alone simulations and in Aspen Dynamics – Simulink co-simulations to control the feed tank level, reboiler level, reflux drum level and top stream pressure of column by adjusting feed 2 flowrate, coolant flowrate to condenser, bottom (Toluene and Phenol) flowrate and product (MCH) flowrate. Then a new controller was developed in Aspen Dynamics and co-simulation to control the product (MCH) purity by adjusting entrainer (Phenol) flowrate. Advanced controller (DMC) has tried to be developed in co-simulation to replace PI controller. However, attempts to develop DMC had failed after few trials. All conventional controllers were tuned using auto tuning method in Aspen Dynamics using a special tool, which is 'tuning' tool. It gives the best control parameters to achieve the best possible control response. Set point changes and disturbance changes have been made to PI controllers and variables respectively, and it is intended to investigate the effect on product purity. The new controller is very helpful in improving the level of product purity. All run shows that Aspen Dynamics stand alone, or co-simulation gives the same results in every test. Before developing Dynamics Model control (DMC) in co-simulation, DMC examples exercises from ‘ENG 420’ was implemented on a simple first order system in MATLAB to understand the basics of the predictive control strategy along with the effect of design parameters. All results obtained are discussed in Section Results and Discussion. Guideline for the next thesis student has been outlined at the end of this report. Overall, most of the main objectives of this thesis was achieved with very satisfying results. However due to unforeseen circumstances and time constraints, DMC controller is not fully functional.

The modern concept of "biorefinery" is dominantly based on chemical pulp mills to create more value than cellulose pulp fibres, and energy from the dissolved lignins and hemicelluloses. This concept is characterized by the conversion of biomass into various biobased products. It includes thermochemical processes such as gasification and fast pyrolysis. In mechanical pulp mills, the feedstock available to the gasification-based biorefinery is significant, including logging residues, bark, fibre material rejects, biosludges and other available fuels such as peat, recycled wood, and paper products. This work is to study co-production of bio-automotive fuels, biopower, and steam via gasification in the context of the mechanical pulp industry.   Biomass gasification with steam in a dual-fluidized bed gasifier (DFBG) was simulated with ASPEN Plus. From the model, the yield and composition of the syngas and the contents of tar and char can be calculated. The model has been evaluated against the experimental results measured on a 150 KWth Mid Sweden University (MIUN) DFBG. The model predicts that the content of char transferred from the gasifier to the combustor decreases from 22.5 wt.% of the dry and ash-free biomass at gasification temperature 750 ℃ to 11.5 wt.% at 950 ℃, but is insensitive to the mass ratio of steam to biomass (S/B). The H2 concentration is higher than that of CO under normal DFBG operating conditions, but they will change positions when the gasification temperature is too high above about 950 ℃, or the S/B ratio is too far below about 0.15. The biomass moisture content is a key parameter for a DFBG to be operated and maintained at a high gasification temperature. The model suggests that it is difficult to keep the gasification temperature above 850 ℃ when the biomass moisture content is higher than 15.0 wt.%. Thus, a certain amount of biomass needs to be added in the combustor to provide sufficient heat for biomass devolatilization and steam reforming. Tar content in the syngas can also be predicted from the model, which shows a decreasing trend of the tar with the gasification temperature and the S/B ratio. The tar content in the syngas decreases significantly with gasification residence time which is a key parameter.   Mechanical pulping processes, as Thermomechanical pulp (TMP), Groundwood (SGW and PGW), and Chemithermomechanical pulp (CTMP) processes have very high wood-to-pulp yields. Producing pulp products by means of these processes is a prerequisite for the production of printing paper and paperboard products due especially to their important functional properties such as printability and stiffness. However, mechanical pulping processes consume a great amount of electricity, which may account for up to 40% of the total pulp production cost. In mechanical pulping mills, wood (biomass) residues are commonly utilized for electricity production through an associated combined heat and power (CHP) plant. This techno-economic evaluation deals with the possibility of utilizing a biomass integrated gasification combined cycle (BIGCC) plant in place of the CHP plant. Integration of a BIGCC plant into a mechanical pulp production line might greatly improve the overall energy efficiency and cost-effectiveness, especially when the flow of biomass (such as branches and tree tops) from the forest is increased. When the fibre material that negatively affects pulp properties is utilized as a bioenergy resource, the overall efficiency of the system is further improved. A TMP+BIGCC mathematic model is developed based on ASPEN Plus. By means of this model, three cases are studied:   1) adding more forest biomass logging residues in the gasifier, 2) adding a reject fraction of low quality pulp fibers to the gasifier, and 3) decreasing the TMP-specific electricity consumption (SEC) by up to 50%.   For the TMP+BIGCC mill, the energy supply and consumption are analyzed in comparison with a TMP+CHP mill. The production profit and the internal rate of return (IRR) are calculated. The results quantify the economic benefit from the TMP+BIGCC mill.   Bio-ethanol has received considerable attention as a basic chemical and fuel additive. It is currently produced from sugar/starch materials, but can also be produced from lignocellulosic biomass via a hydrolysis--fermentation or thermo-chemical route. In terms of the thermo-chemical route, a few pilot plants ranging from 0.3 to 67 MW have been built and operated for alcohols synthesis. However, commercial success has not been achieved. In order to realize cost-competitive commercial ethanol production from lignocellulosic biomass through a thermo-chemical pathway, a techno-economic analysis needs to be done.   In this work, a thermo-chemical process is designed, simulated, and optimized mainly with ASPEN Plus. The techno-economic assessment is made in terms of ethanol yield, synthesis selectivity, carbon and CO conversion efficiencies, and ethanol production cost.   Calculated results show that major contributions to the production cost are from biomass feedstock and syngas cleaning. A biomass-to-ethanol plant should be built at around 200 MW. Cost-competitive ethanol production can be realized with efficient equipments, optimized operation, cost-effective syngas cleaning technology, inexpensive raw material with low pretreatment cost, high-performance catalysts, off-gas and methanol recycling, optimal systematic configuration and heat integration, and a high-value byproduct.

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.

Submitted by Isaac Francisco de Souza Dias (isaac.souzadias@ufpe.br) on 2015-05-18T18:24:59Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE - Thibério - Parte escrita - 81 - FINAL.pdf: 8671428 bytes, checksum: 626d3d6a70a811bf559ef1ba89a7d967 (MD5)<br>Made available in DSpace on 2015-05-18T18:24:59Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE - Thibério - Parte escrita - 81 - FINAL.pdf: 8671428 bytes, checksum: 626d3d6a70a811bf559ef1ba89a7d967 (MD5) Previous issue date: 2015-04-04<br>CAPES<br>Nos últimos anos o biodiesel se tornou uma alternativa para a demanda crescente de combustível no país e no mundo. O próximo passo é conseguir produzir um biodiesel economicamente competitivo com o diesel fóssil em um processo a nível industrial. Uma tecnologia que vem ganhando espaço ultimamente é a destilação reativa. O objetivo deste trabalho foi estudar do ponto de vista computacional e experimental a produção de biodiesel por destilação reativa. Para isso, foi construída uma coluna piloto com 1,5 m de altura em vidro, dotada de toda parte de controle automático para a aquisição de dados. Foi utilizado o Aspen Plus® para realizar as simulações com base nos resultados obtidos experimentalmente. Também foi realizado neste trabalho uma modelagem cinética da transesterificação do óleo de algodão em rota etílica a fim de se obter parâmetros da reação para serem inseridos no simulador. Em seguida, foi comparada a viabilidade da rota etílica com a metílica via simulação e sugerido um processo de extração com o próprio glicerol. Os resultados mostraram que a destilação reativa apresenta melhor desempenho quando comparado a outros processos como por exemplo reatores PFR também estudados neste trabalho. Por fim, foi sugerido um projeto de uma coluna de destilação reativa, extrativa e absortiva para a produção de biodiesel.

In recent years, there is a rapid growing interest in the use of biomethane for the transport sector. A new method of combining anaerobic digestion and biomass gasification is proposed.The feasibility study shows that more biomethane can be produced; resulting in an increase in the revenue compared to individual biogas plants. The GoBiGas project,which is initiated by Göteborg Energi, adopted another method based on gasification, water gas shift and methanation to enable biomethane production from forest residue. The aim of the present study is to investigate the economic viability of the new method when compared with the GoBiGas (Gothenburg Biomass Gasification) process. For this study, a model of GoBiGas process was developed in Aspen Plus to perform the technical analysis, in which the overall efficiency and exergy efficiency were calculated at different moisture contents of biomass. For the economic analysis, the annual revenue was also estimated during the study. The results show that the overall efficiency of the new method is higher than the efficiency of the GoBiGas process and there is more production of biomethane from the new process.

Submitted by Lucienne Costa (lucienneferreira@ufcg.edu.br) on 2018-04-12T14:56:31Z No. of bitstreams: 1 ALAIN CHARLES DE MELO ALVES - DISSERTAÇÃO (PPGEQ) 2017.pdf: 2958576 bytes, checksum: da6d8a9342aea19b0bd4eb2403563d7c (MD5)<br>Made available in DSpace on 2018-04-12T14:56:31Z (GMT). No. of bitstreams: 1 ALAIN CHARLES DE MELO ALVES - DISSERTAÇÃO (PPGEQ) 2017.pdf: 2958576 bytes, checksum: da6d8a9342aea19b0bd4eb2403563d7c (MD5) Previous issue date: 2017-02-17<br>Capes<br>Os processos indústrias em sua maioria são multivariáveis e apresentam uma grande interação entre suas variáveis. A fim de reduzir essas interações algumas técnicas têm sido desenvolvidas. Análise de Componentes Independentes (ICA) tem sido uma técnica bastante promissora quando se deseja reduzir ou até mesmo eliminar o acoplamento entre as variáveis. Essa técnica é usada na separação de fontes desconhecidas. Embora já existam diversos trabalhos recentes sobre a aplicação do ICA em processos industriais, poucos são voltados para aplicação da técnica em colunas de destilação. Este trabalho estabelece uma estratégia de controle aplicado a uma coluna de destilação de alta pureza com recompressão de vapor utilizando o ICA. Além disso, o trabalho estabeleceu uma estratégia de controle para as composições de base e topo. Para tanto foi feita uma comunicação entre o Aspen Plus DynamicsTM e o Simulink/Matlab®. A comunicação foi estabelecida por meio do bloco AMSimulation. Duas estratégias de controle foram comparadas: MPC com o ICA e MPC sem o ICA. Os resultados da estratégia MPC com ICA se apresentaram mais promissoras mostrando que a técnica ICA é uma ferramenta desacoplante útil para sistemas com forte acoplamento.<br>The industrial processes are in its majority are multivariable and show a high number of interactions between its variables. Some techniques have been developed to target the reduction of these interactions. Independent Component Analysis (ICA) has been a very promising technique when it is desired to reduce or even eliminate the coupling between variables. The ICA technique has been utilized on the separation of unknown sources. Although there are several different studies targeting the application of ICA in industrial processes, just a few of them geared for technical applications in distillation columns. This dissertation attempts to establish a control strategy applied to a high purity distillation column with vapor recompression using the ICA. In addition, the dissertation proposes to establish a control strategy for the bottom and top of compositions. For this will be a communication between the Aspen Plus DynamicsTM and Simulink / Matlab®. The communication will be established through the AMSimulation block. Two control strategies were compared: MPC with ICA and MPC without MPC. The results of the MPC with ICA strategy were shown to be more promising, showing that the ICA technique is a useful decoupling tool for systems with strong coupling.

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.

Carbon dioxide is considered to be the major source of GHG responsible for global warming; man-made CO₂ contributes approximately 63. 5% to all greenhouse gases. The cement industry is responsible for approximately 5% of global anthropogenic carbon dioxide emissions emitting nearly 900 kg of CO₂ for every 1000 kg of cement produced! Amine absorption processes in particular the monoethanolamine (MEA) based process, is considered to be a viable technology for capturing CO₂ from low-pressure flue gas streams because of its fast reaction rate with CO₂ and low cost of raw materials compared to other amines. However, MEA absorption process is associated with high capital and operating costs because a significant amount of energy is required for solvent regeneration and severe operating problems such as corrosion, solvent loss and solvent degradation. This research was motivated by the need to design size and cost analysis of CO₂ capture process from cement industry. MEA based absorption process was used as a potential technique to model CO₂ capture from cement plants. In this research four cases were considered all to reach a CO₂ purity of 98% i) the plant operates at the highest capacity ii) the plant operates at average load iii) the plant operates at minimum operating capacity and iv) switching to a lower carbon content fuel at average plant load. A comparison among four cases were performed to determine the best operating conditions for capturing CO₂ from cement plants. A sensitivity analysis of the economics to the lean loading and percent recovery were carried out as well as the different absorber and striper tray combinations.

Orientador: Rubens Maciel Filho, Maria Regina Wolf Maciel<br>Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica<br>Made available in DSpace on 2018-08-09T09:35:16Z (GMT). No. of bitstreams: 1 Custodio_AlineFerrao_D.pdf: 2173448 bytes, checksum: 27b046c8dc2de1781ef672eb1c4ab063 (MD5) Previous issue date: 2007<br>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<br>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<br>Doutorado<br>Desenvolvimento de Processos Químicos<br>Doutor em Engenharia Química

Coal is the dominant and most reliable source of energy in Australia. However, the increasing global temperatures and its impact on the climate raises concerns on the use of coal worldwide. Due to availability of abundant, cheap quality coals, Australia is researching how it and its international customers can continue to use its abundant coal resources whilst limiting greenhouse emissions. Hence, low CO2 emitting energy technologies like carbon capture and storage (CCS) have an important role to play not only in power but also the cement and steel industries Post-combustion CO2 capture (PCC), the most developed technology in CCS using aqueous amines to capture CO2, still face challenges for its large-scale commercialisation. The cost of electricity with PCC rises to almost double that produced without integrating PCC technology in new power stations. The retrofit of PCC technology into existing power stations is very site specific and costs can be around half of the cost of building a new power plant. Apart from this, the implementation of PCC poses an energy penalty to the power station as the efficiency of the plant can drop almost by 10-11% due to the increased solvent heating and CO2 compression loads. Particularly with the nations like Australia, the cost of PCC installation is even higher as there are no flue gas desulfurisation (FGD) units in Australian power stations. The presence of harmful gases like SO2 in coal-fired power plant flue gases affect CO2 capture performance during PCC due to the higher affinity of amines to absorb stronger acidic gases against CO2 which is a weaker acid gas than SO2. These stronger acidic gases tend to form heat stable salts with the absorbent amines used to capture CO2 . Heat stable salts refer to the thermally non-regenerable protonated amines which are usually produced when the amine solution is contaminated by organic acids (Weiland et al., 2004). Hence, the bonded amine is not available for CO2 capture, increasing the requirement for makeup amine resulting in higher operating cost. Therefore, FGD units are an essential requirement before the installation of PCC facilities in a coal-fired power station. This results in a levelised cost of electricity in Australian power plants that is high compared to nations which have FGD installed in their power stations. CSIRO has developed a combined capture process to simultaneously capture CO2 and SO2 from Australian power plant flue gases using a single amine absorbent in order to lower the cost of PCC installation in Australia. The process generates a unique sulfur rich amine absorbent which needs regeneration. This thesis investigates various amine regeneration processes, using MEA as a reference, and their commercial viability to the CS-Cap process. Due to the unique nature of the sulfur rich absorbent generated in the CS-Cap process, its amine is recoverable through many other regeneration processes besides standard thermal reclamation. My thesis investigates the effectiveness of regeneration techniques like Ion exchange, Electro-dialysis, Crystallisation, Nano-filtration in regenerating the sulfur rich amine. Initially the theoretical investigation was carried as a part of literature review and further a brief exploratory laboratory scale evaluation of the most suited technologies was carried out. The results obtained from laboratory scale experimentation were fed to an Aspen Plus simulation model in order to understand the behaviour of the system under various operating conditions. Further a cost estimation was carried out in order to produce a high level cost for the selected regeneration technologies in the CS-Cap process. The cost of the regeneration technologies were further integrated into the overall CO2 capture process in order to compare the cost of standard FGD + PCC process against the CS-Cap process which answers the broader research question whether the CS-Cap process will be economical for Australian coal power plants. Overall this thesis reveals the effectiveness of various technologies in regenerating sulfur rich amines. It suggests CSIRO’s patented CS-Cap process is a cost-effective approach for capturing CO2 from Australian coal fired power plants despite its sensitivity to regeneration cost.<br>Doctor of Philosophy

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.

Orientador: Rubens Maciel Filho<br>Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química<br>Made available in DSpace on 2018-08-23T11:34:50Z (GMT). No. of bitstreams: 1 Maia_JulioPereira_D.pdf: 8705466 bytes, checksum: e604d7a471ca19eb99492912d431174b (MD5) Previous issue date: 2013<br>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<br>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<br>Doutorado<br>Desenvolvimento de Processos Químicos<br>Doutor em Engenharia Química

Les boues d'eaux usées des moulins à huile (OMWS) constituent un problème environnemental majeur pour les pays producteurs d'huile d'olive. Diverses stratégies d'élimination des OMWS ont été proposées, en particulier la pyrolyse rapide qui est considérée comme une technique prometteuse et dont le principal produit est la bio-huile qui trouve son application comme diesel vert dans les moteurs à combustion interne. Dans la pyrolyse rapide, les vapeurs de bio-huile sont refroidies en utilisant une machine de réfrigération à compression. L'objectif de la thèse est d'intégrer une machine de réfrigération par absorption en récupérant la chaleur du processus, en se substituant à la machine de réfrigération par compression et réduisant ainsi la consommation d'électricité. Il s'avère que le procédé de réfrigération par sorption permet une meilleure efficacité énergétique. Le ratio exergie de la bio-huile sur exergie électrique passe de 27 à 102 du système conventionnel au système à sorption. Une analyse économique est effectuée pour déterminer le prix de vente minimum de la bio-huile en tant que combustible (MFSP). Il est observé que le MFSP est réduit de 3,63 €/GGE à 2,99 €/GGE entre le système conventionnel au système à sorption. La différence provient de la consommation d’énergie électrique évitée. L’analyse de sensibilité économique met en évidence que le coût de production de la bio huile diminue plus rapidement que l’augmentation du coût d’investissement induit par cette augmentation de production<br>Oil mill sewage sludge (OMWS) is a major environmental problem for olive oil producing countries. Various OMWS elimination strategies have been proposed, in particular rapid pyrolysis which is considered a promising technique and whose main product is bio-oil which finds its application as green diesel in internal combustion engines.In rapid pyrolysis, bio-oil vapors are cooled using a compression refrigeration machine. The objective of the thesis is to integrate an absorption refrigeration machine by recovering the heat of the process, replacing the compression refrigeration machine and thus reducing electricity consumption.It turns out that the sorption refrigeration process allows for better energy efficiency. The ratio of bio-oil exergy to electrical exergy goes from 27 to 102 from the conventional system to the sorption system.An economic analysis is performed to determine the minimum selling price of bio-oil as fuel (MFSP). It is observed that the MFSP is reduced from 3.63 € / GGE to 2.99 € / GGE between the conventional system and the sorption system. The difference comes from the electricity consumption avoided. The economic sensitivity analysis shows that the production cost of bio oil decreases more rapidly than the increase in the investment cost induced by this increase in production

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.<br>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.

Ce travail de recherche porte sur la modélisation mathématique des principaux procédés sidérurgiques en suivant une approche systémique. L’objectif est d’élaborer un outil de modélisation de l’ensemble de la filière destiné à l’optimiser du point de vue énergétique et environnemental. Nous avons développé des modèles physico-chimiques du haut fourneau, de la cokerie, de l’agglomération et du convertisseur. Ces modèles ont ensuite été reliés entre eux sous forme d’un diagramme de flux unique en utilisant le logiciel ASPEN Plus. Dans une première partie, nous nous sommes particulièrement intéressés au haut fourneau à recyclage, une variante innovante du haut fourneau dans laquelle les gaz de gueulard sont recyclés et réinjectés aux tuyères après capture du CO2. Nous avons testé une réinjection à un niveau (aux tuyères) et à deux niveaux (tuyères et ventre). Les résultats ont été comparés avec succès à des données expérimentales issues d’un réacteur pilote et montrent que le recyclage permet une baisse de plus de 20 % des émissions de CO2 du haut fourneau. Le recyclage à deux niveaux ne semble pas plus performant que celui à un seul niveau. Dans un deuxième temps, nous avons simulé le fonctionnement d’une usine sidérurgique intégrée dans son ensemble. Différentes configurations ont été testées, pour un haut fourneau classique ou un haut fourneau à recyclage, en considérant un éventuel recyclage du laitier de convertisseur à l’agglomération, et en étudiant l’influence de la teneur en silicium de la fonte sur toute la filière. On montre notamment qu’il est possible de réduire le prix de revient de la tonne d’acier en substituant et recyclant différents sous-produits<br>This research study deals with mathematical modeling of the main steelmaking processes following a systems approach. The objective was to build a modeling tool of the whole steelmaking route devoted to its energetic and environmental optimization. We developed physical-chemical models for the blast furnace, the coke oven, the sintering plant and the basic oxygen furnace. These models were then linked together in a single flow sheet using the ASPEN Plus software. First, we focused on the top gas recycling blast furnace, a novel variant of the blast furnace in which the top gas is recycled and re-injected into the tuyeres after CO2 removal and capture. We tested both a reinjection at one level (tuyeres only) and at two levels (tuyeres and shaft). The results were successfully compared with experimental data from a pilot reactor and demonstrate that recycling can lower the blast furnace CO2 emissions by more than 20%. Recycling at two levels does not seem more efficient than at a single level. Second, we simulated the operation of an entire integrated steelmaking plant. Different configurations were tested, using a conventional blast furnace or a top gas recycling blast furnace, considering a possible recycling of the converter slag to the sintering plant, and studying the influence of Si content in the hot metal on the entire steelmaking plant operation. We show that it is possible to reduce the cost of producing steel by substituting and recycling various by-products

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<br>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

Submitted by repositorio repositorio (repositorio@unifei.edu.br) on 2016-06-02T18:05:55Z No. of bitstreams: 1 dissertacao_nasner_2015.pdf: 2757814 bytes, checksum: 78e458c84cc6a7fb5734fb9d4c5631e7 (MD5)<br>Made available in DSpace on 2016-06-02T18:05:55Z (GMT). No. of bitstreams: 1 dissertacao_nasner_2015.pdf: 2757814 bytes, checksum: 78e458c84cc6a7fb5734fb9d4c5631e7 (MD5) Previous issue date: 2015-03<br>A recuperação de energia dos Resíduos Sólidos Urbanos (RSU) tem sido amplamente desenvolvida no mundo, porém, cada vez a proteção ambiental se torna mais importante e o controle das emissões de incineração dos RSU também se torna mais significativo. Para proporcionar uma solução energética mais eficiente e amigável ambientalmente, o estudo da tecnologia de gaseificação dos RSU, processo atrativo por diminuir a possibilidade de formação de substancias como dioxinas e furanos tem ganhado importância. Neste trabalho apresenta-se a modelagem de uma planta piloto de gaseificação em leito fixo concorrente do Combustível Derivado de Resíduo (CDR), utilizando ar como agente de gaseificação, num sistema integrado a motor de combustão interna ciclo Otto. O CDR é obtido através da triagem, secagem, moagem e compactação dos RSU. O modelo foi desenvolvido no software Aspen Plus™, visando prever as condições de operação ideais para atingir a máxima eficiência. O pacote termodinâmico NRTL e a equação de estado de Hayden−O’Connell, foram utilizados na simulação. O modelo é baseado na minimização da energia livre de Gibbs em equilíbrio para fornecer resultados relativos à produção do gás de gaseificação (syngas). Os resultados indicaram que a Relação de Equivalência (RE) exerce influência direta na temperatura do gaseificador e a composição do gás produzido. Os efeitos desta variável sobre o poder calorífico (PCI) e a eficiência a frio do gás de gaseificação (CGE) foram discutidos. Para os valores de RE entre 0,25-0,3; e de temperaturas entre 680 e 700°C, foi atingida a máxima eficiência CGE, compreendida entre 57-60%. Dessa maneira, obteve-se um gás de gaseificação com um PCI de 5,8 MJ/Nm³, o qual se encontra na faixa dos valores médios esperados, quando o fluído de gaseificação é ar. O gás de gaseificação obtido foi queimado num motor de combustão interna, atingindo uma potência elétrica de 50 kWe. Uma análise econômica da implementação da Planta Piloto também foi realizada, mostrando que o projeto é viável a partir de uma potência de 150kWe, com um investimento inicial de aproximadamente R$ 1,1 milhões de reais.

The research demonstrated a balanced process, energy, and techno-economic argument for the utilisation of concentrated solar thermal energy, essentially, for hydrogen production and other industrial process systems. The representative case studies undertaken in the research addressed process and solar thermal energy modelling, energy integration, process optimisation, exergy assessment, and techno-economic evaluation as it relates to renewable hydrogen and hydrogen-based fuel production. The research established that economic assessment studies, process-energy configuration, choice of renewable energy, and mixed energy options are key to the shift from fossil fuel to green energy and industrial production to significantly reduce the impact of climate change.

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.

In this study a supercritical fluid extraction process using carbon dioxide as a solvent was developed and investigated as a potential energy efficient and cost effective alternative to conventional distillation for the extraction and subsequent fractionation of high value renewable chemicals from lignocellulosic bio-oil. Fundamental solubility studies utilizing both laboratory and pilot infrastructure were completed, and equation of state modelling and process simulations developed for the first time for this supercritical fluid extraction process. Techno-economic evaluation of the processes revealed that supercritical fluid extraction of bio-oil is a competitive alternate to conventional distillation process.

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 &amp; 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 &amp; 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 &amp; 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.

This dissertation describes the design and optimization of a CO2-capture unit using aqueous amines to remove of carbon dioxide from the flue gas of a coal-fired power plant. In particular we construct a monolithic model of a carbon capture unit and conduct a rigorous optimization to find the lowest solvent regeneration energy yet reported. Carbon capture is primarily motivated by environmental concerns. The goal of our work is to help make carbon capture and storage (CCS) a more efficient for the sort of universal deployment called for by the Intergovernmental Panel on Climate Change (IPCC) to stabilize anthropomorphic contributions to climate change, though there are commercial applications such as enhanced oil recovery (EOR). We employ the latest simulation tools from Aspen Tech to rigorously model, design, and optimize acid gas systems. We extend this modeling approach to leverage Aspen Plus in the .NET framework through Microsoft's Component Object Model (COM). Our work successfully increases the efficiency of acid gas capture. We report a result optimally implementing multiple energy-saving schemes to reach a thermal regeneration energy of 1.67 GJ/tonne. By contrast, the IPCC had reported that leading technologies range from 2.7 to 3.3 GJ/tonne in 2005. Our work has received significant endorsement for industrial implementation by the senior management from the world's second largest chemical corporation, Sinopec, as being the most efficient technology known today.<br>Ph. D.

Thesis (PhD)--Stellenbosch University, 2014.<br>ENGLISH ABSTRACT: Data on the process performance at different operating conditions are required to determine the feasibility of a separation process. Such data can be experimentally measured, but due to the time and costs associated with pilot plant scale experiments, the use of predictive process models are often preferred. The main aim of this project is to establish a working process model in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process aimed at the separation of mixtures of detergent range alkanes and alcohol isomers where similar boiling points or low relative volatilities can occur. Currently, an azeotropic distillation process is employed for the separation of detergent range alkanes and alcohols. Although this process shows good separation performance, some concerns regarding the operating conditions are raised: the preferred entrainer, diethylene glycol, is toxic to humans; very low operating pressures of 0.016 – 0.031 MPa and high temperatures of 473 K are required; additional processing units and materials are required to remove the entrainer from the product streams. An alternative process, supercritical fluid fractionation, is proposed in this work after previous studies have reported that this process have potential for the separation of alkanes and alcohols. The supercritical fluid fractionation process addresses the concerns of the azeotropic distillation process in the following ways: a non-toxic solvent, CO2, is used as the separating agent; mild temperatures of 344 K is proposed, but at the cost of the low operating pressures of the azeotropic process; and a single process unit and no additional material is required to separate the solvent from the product streams. A process model was developed in Aspen Plus® to evaluate the separation performance of the newly proposed supercritical fluid fractionation process and compare it to the current azeotropic distillation process. The development of the process model included the development of an accurate thermodynamic model in Aspen Plus®. After thorough evaluation of a number of cubic equations of state, the RK-ASPEN model was found to be superior in its representation and prediction of phase transition pressures for multi-component mixtures of detergent range alkanes and alcohols in the temperature range 318 – 348 K. Phase transition pressures could be predicted with an error of less than 6 % with the inclusion of regressed polar parameters and binary solute-solvent interaction parameters for two multi-component mixtures: CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) and CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol). Polar parameters were regressed from pure component vapour pressure data predicted with correlations available in Aspen Plus®. Binary interaction parameters were regressed from experimental bubble and dew point data. Binary bubble and dew point data were measured for a number of systems containing ethane or CO2 and a C10-alkane or C10-alcohol isomer at temperatures between 308 K and 353 K, and compositions ranging between 0.01 and 0.7 mass fraction solute. A comparison between the phase equilibrium data measured for these systems revealed that the structure of the molecule, and not only the molecular weight, influences its solubility in the supercritical solvent. The phase transition pressures of n-decane, 2-methylnonane, 3-methylnonane and 4-methylnonane did not differ significantly in CO2 or ethane, and these compounds will in all likelihood not be separated in a supercritical fluid fractionation process. The phase transition pressures measured for the C10-alcohol isomers decreased in both CO2 and ethane in the following order: 1-decanol, 3,7-dimethyl-1-octanol, 2-decanol, 2,6-dimethyl-2-octanol and 3,7-dimethyl-3-octanol. The position of the hydroxyl group and the number, length and position of the side branches, all influence the solubility behaviour and phase transition pressures of the isomeric alcohols in the supercritical solvent. Since the use of ethane did not show any significant benefits with regard to selectivity, the use of the less harmful and less expensive solvent, CO2, in further investigations was justified. The RK-ASPEN thermodynamic model, with the inclusion of the regressed polar and binary solute-solvent interaction parameters, was implemented in the process model and the separation performance of the process was simulated at different operating conditions for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) mixture. A comparison to experimental pilot plant data revealed that the model cannot be used to predict the separation performance at low fractionation temperatures (316 K) due to shortcomings in the thermodynamic model. However, the performance of the process at high fractionation temperatures (344 K) could be predicted well, with an error of 10 – 36 %. Simulations for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) mixtures showed that the composition of the feed mixture have a significant effect on the location and size of the operating window and optimum operating conditions. The optimum operating conditions were defined as the conditions where an acceptable selectivity ratio and alcohol recovery occurred simultaneously. Since the selectivity ratio and alcohol recovery have opposing optimization approaches, a number of possible optimum operating conditions exist, based on the product specifications. When an alcohol and an alkane with similar phase behaviour exist in a mixture, a distinct minimum selectivity ratio will occur at a point within the extract-to-feed ratio limits of the process. When the alkanes and alcohols present in a mixture do not have similar or overlapping phase transition pressures, the minimum selectivity ratio will typically cover a small range of extract-to-feed ratios at the high end limit of the extract-to-feed ratio range. To summarize: A process model was established in Aspen Plus® that can be used to determine the feasibility and separation performance of a supercritical fractionation process for a feed mixture of detergent range alkane and alcohol isomers. The model was used to prove that an SFF process is a feasible alternative process to consider for the removal of alkanes from mixtures of detergent range alcohol isomers, even where overlapping boiling points or low relative volatilities occur. During the development of the process model, the following significant novel contributions were made: · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical ethane, as published in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical CO2, as published in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · A thermodynamic model was developed in Aspen Plus® that can accurately predict the phase transition pressures of binary, ternary and multi-component mixtures of detergent range alkanes and alcohols in supercritical CO2, as published in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · A process model was developed in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process for the separation of mixtures of detergent range alkanes and alcohols. · Experimental and simulated results indicated that a supercritical fluid fractionation process can be implemented successfully to separate an alkane from a mixture of alcohol isomers, as was shown for two mixtures: CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol).<br>AFRIKAANSE OPSOMMING: Data oor die omvang van skeiding by verskillende bedryfstoestande word benodig om die lewensvatbaarheid van ’n skeidingsproses te bepaal. Sulke data kan eksperimenteel gemeet word, maar as gevolg van die tyd en kostes geassosieer met eksperimente op loodsaanlegskaal, word die gebruik van prosesmodelle verkies. Die hoofdoel van hierdie projek is om ’n werkende prosesmodel, wat daarop gemik is om C8 – C20 alkane en alkohol isomere te skei, in Aspen Plus® tot stand te bring om die omvang van die skeiding van ’n superkritiese fraksioneringsproses te meet. Tans word azeotropiese distillasie gebruik vir die skeiding van C8 – C20 alkane en alkoholisomere. Alhoewel goeie skeiding met hierdie proses bewerkstellig word, is daar sekere eienskappe van die proses wat aandag vereis: die voorgestelde skeidingsagent, dietileen glikol, is giftig vir mense; baie lae bedryfsdrukke van 0.016 – 0.031 MPa en hoë temperature van 473 K word benodig; addisionele proseseenhede en materiaal is nodig om die skeidingsagent van die produkte te verwyder. Die gebruik van ’n alternatiewe proses - superkritiese fraksionering - word in hierdie werk voorgestel nadat vorige studies getoon het dat hierdie proses die potensiaal het om alkane en alkohole te skei. Die superkritiese fraksioneringsproses spreek al die kommerwekkende eienskappe van azeotropiese distillasie aan soos volg: ’n veilige oplosmiddel, CO2, word as die skeidingsagent gebruik; gemiddelde temperature van 344 K word voorgestel, maar ten koste van lae bedryfsdrukke; ’n enkele proseseenheid en geen addisionele materiaal word benodig om die oplosmiddel van die produkte te skei nie. ’n Prosesmodel is in Aspen Plus® ontwikkel om die omvang van die skeiding wat deur die voorgestelde superkritiese fraksioneringsproses teweeggebring is, te evalueer en te vergelyk met die azeotropiese distillasieproses wat tans in gebruik is. Die ontwikkeling van die prosesmodel sluit die ontwikkeling van ’n akkurate termodinamiese model in Aspen Plus® in. Na deeglike evaluasie van ’n aantal kubiese toestandsvergelykings is gevind dat die RK-ASPEN-model die faseoorgangsdrukke van multi-komponentmengsels van C8 – C20 alkane en alkohole die beste voorspel binne die temperatuurbereik van 318 – 348 K. Faseoorgangsdrukke kon voorspel word met ’n fout van minder as 6 % met die insluiting van voorafbepaalde polêre parameters en binêre interaksie-parameters vir twee multi-komponentmengsels: CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) and CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol). Polêre parameters is bepaal met dampdruk data, wat voorspel is met korrelasies in Aspen Plus®. Binêre interaksieparameters is van eksperimentele faseoorgangsdata bepaal. Binêre faseoorgangsdata is vir ’n aantal sisteme wat uit etaan of CO2 en ’n C10-alkaan- of C10-alkohol-isomeer bestaan, gemeet by temperature tussen 308 K en 353 K en samestellings van tussen 0.01 en 0.7 massafraksie van die opgeloste stof. ’n Vergelyking tussen die gemete fase-ewewigsdata het onthul dat die struktuur van die molekuul, en nie net die molekulêre massa nie, die oplosbaarheid van die stof in die superkritiese oplosmiddel beïnvloed. Die faseoorgangsdrukke van n-dekaan, 2-metielnonaan, 3-metielnonaan en 4-metielnonaan het geen skynbare verskille getoon in etaan of CO2 nie en dus sal hierdie stowwe in alle waarkynlikheid nie met ’n superkritiese fraksioneringsproses geskei kan word nie. Die faseoorgangsdrukke wat vir die C10-alkohol gemeet is, het in beide etaan en CO2 afgeneem in die volgende volgorde: 1-dekanol, 3,7-dimetiel-1-oktanol, 2-dekanol, 2,6-dimetiel-2-oktanol en 3,7-dimetiel-3-oktanol. Die posisie van die hidroksielgroep en die aantal, lengte en posisie van die sytakke beïnvloed die oplosbaarheidsgedrag van die alkohol-isomere in die superkritiese oplosmiddel. Aangesien die gebruik van etaan nie enige voordele ten opsigte van selektiwiteit inhou nie, is die gebruik van die minder skadelike en goedkoper oplosmiddel, CO2, vir verdere ondersoeke geregverdig. Die ontwikkelde termodinamiese model, met die insluiting van die polêre parameters en binêre interaksieparameters, is in die prosesmodel ingesluit en die omvang van die skeiding van die proses is gesimuleer by verskillende bedryfstoestande vir die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) mengsel. ’n Vergelyking tussen die gesimuleerde data en die eksperimentele loodsaanlegdata het onthul dat die model nie die omvang van die skeiding kan voorspel by lae fraksioneringstemperature (316 K) nie as gevolg van die tekortkominge in die termodinamiese model. Die omvang van die skeiding by hoë temperature (344 K) kon egter goed voorspel word met ’n fout van 10 – 36 %. Simulasies van die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) mengsels het getoon dat die samestelling van die voermengsel ’n beduidende effek op die grootte van die bedryfsvenster en optimum bedryfstoestande het. Die optimum bedryfstoestande word gedefinieer as die toestande waar ’n aanvaarbare selektiwiteitsverhouding en alkoholherwinning terselfdertyd voorkom. Aangesien die selektiwiteitsverhouding en alkoholherwinning teenstrydige optimeringsbenaderings het, bestaan daar ’n aantal optimum bedryfstoestande gebaseer op die produkspesifikasies. Wanneer ’n alkohol en ’n alkaan met ooreenstemmende fasegedrag saam in ’n mengsel voorkom, bestaan daar ’n duidelike minimum selektiwiteitsverhouding by ’n punt binne die ekstrak-tot-voer-verhoudingslimiete van die proses. Wanneer die alkane en alkohole in ’n mengsel nie ooreenstemmende fasegedrag toon nie, sal die minimum selektiwiteitsverhouding oor ’n reeks ekstrak-tot-voer-verhoudings voorkom, tipies by die hoë limiet van die ekstrak-tot-voer-verhoudingsreeks. Om op te som: ’n Prosesmodel is in Aspen Plus® tot stand gebring wat die lewensvatbaarheid en omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses vir voermengsels van C8 – C20 alkane en alkohol-isomere kan voorspel. Die model is gebruik om te bewys dat ’n superkritiese proses ’n lewensvatbare alternatiewe proses is om te oorweeg vir die verwydering van alkane uit mengsels van alkohol-isomere, self waar ooreenstemmende kookpunte of lae relatiewe vlugtigheid tussen komponente voorkom. Tydens die ontwikkeling van die prosesmodel is die volgende beduidende nuwe bydraes gemaak: · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan- en C10-alkohol-isomere in superkritiese etaan, soos gepubliseer in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan and C10-alkohol isomere in superkritiese CO2, soos gepubliseer in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · ’n Termodinamiese model is ontwikkel in Aspen Plus® wat die faseoorgangsdrukke van binêre, ternêre en multi-komponent mengsels van C8 – C20 alkane en alkohol-isomere in superkritiese CO2 akkuraat kan voorspel, soos gepubliseer in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · ’n Prosesmodel is ontwikkel in Aspen Plus® wat die omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses, gemik op die skeiding van mengsels van C8 – C20 alkane en alkohol-isomere, kan voorspel. · Eksperimentele en gesimuleerde resultate toon aan dat ’n superkritiese fraksioneringsproses suksesvol geïmplementeer kan word vir die skeiding van ’n alkaan vanuit ’n mengsel van alkohol-isomere, soos bewys vir twee mengsels: CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol).

Mestrado em Engenharia Química<br>Este trabalho de dissertação efetuado em ambiente empresarial na unidade de recuperação de solventes EGEO Solventes S.A teve como principal objetivo a otimização das colunas de destilação descontínua através da realização de um estudo da viabilidade de colocação de enchimento e consequente análise e comparação dos resultados obtidos com e sem enchimento. Sendo a EGEO Solventes S.A uma empresa que opera na área de regeneração de solventes, utilizando para este fim equipamento industrial de separação de misturas e, sempre tendo a maximização da eficiência das suas instalações em mente, o estudo efetuado nesta dissertação pretende utilizar as mais valias do software de modelação e simulação de processos de última geração disponível na atualidade de forma a dar resposta a um dos objetivos de melhoria contínua da empresa. Começou-se assim o trabalho por traçar um perfil rigoroso de operação das colunas de destilação descontínua em causa através da recolha de dados de operação das colunas reais preexistentes na empresa, de forma a obter a informação e dados necessários para efetuar cálculos e alimentar o simulador informático que iria ser utilizado no estudo. Escolheu-se dois tipos diferentes de misturas para traçar o perfil de destilação para obter um cenário mais abrangente: um produto frequentemente produzido na empresa para efeitos de comercialização pela própria marca e um produto constituído por uma mistura pouco frequente na empresa e que iria ser retornado ao cliente após tratamento. Foram retirados caudais instantâneos de destilado, temperaturas de cauda, meio, topo e destilado, pressões de operação e de condensação, densidade de destilado, composições de mistura, entre outros dados, permitindo assim ter uma boa base inicial para aproximar as iterações que iriam ser efetuadas no simulador/modelador informático. Com estes dados foi ainda possível efetuar um cálculo de HETP necessário como parâmetro de entrada de relevo na simulação. Posteriormente, procedeu-se à segunda fase do trabalho: Modelação do processo em causa e simulação de colocação de enchimento e posterior comparação de resultados no software Aspen Plus®. Utilizando todos os dados recolhidos anteriormente e convergindo a modelação, através de um processo de cálculo iterativo, para um caso aproximado ao que acontece nas instalações da empresa, foi possível concluir o estudo de viabilidade e apresentar as devidas conclusões. Devido ao diâmetro da secção de colocação de enchimento ser demasiado pequena e devido ao aumento das quedas de pressão associadas à utilização do enchimento, a coluna tem tendência a inundar para a gama de caudais onde o seu funcionamento seria ótimo. Ainda assim, foram efetuados testes para uma gama de caudais inferiores de forma a tentar contornar o problema, mas verificou-se que para essa gama de caudais mais baixos, a coluna irá secar devido ao facto do balanço entre mistura a evaporar e caudal de fase líquida nova a entrar não se verificar, evaporando mais do que se consegue alimentar à coluna a caudais baixos. Das modelações e simulações efetuadas, confirmou-se a inviabilidade de colocação de enchimento nas colunas em causa, mas efetuou-se ainda cálculos de forma a ser possível estimar um valor de diâmetro de secção de enchimento mínimo para cada caudal em estudo. Os valores foram apresentados como sugestão de modificação futura na empresa.<br>The present dissertation made in the company EGEO Solventes S.A, had as major goal the optimization of the single staged discontinuous columns by making a viability study on the usage of packing on said columns and subsequent analysis and result comparison with and without packing usage. Being a company that operates on solvent recovery by using industrial separation equipment, and is always keen on maximizing the overall efficiency of their site, the study done in the present dissertation aims to take advantage on the latest technology available on process simulation and modelling in order to assist the company in the pursuit of one of their main goals: continuous improvement. The work started by rigorously profiling a real single staged discontinuous column to obtain valuable experimental data which was proven fundamental to make some important calculations and to feed the simulator’s input fields that was going to be used in the present study. Two very different kind of dirty mixes were chosen to profiling analysis to reach a wider array of results: A product often produced by the company for selling as a company-branded product, and a new product composed by an unfrequently seen mix that would be returned to the client after processing. It was registered instant distillate volumetric flow rate values, distillate, bottom, mid and top temperatures, operational and condensate pressures, distillate density, mixing compositions, and other miscellaneous data this way allowing to have a good initial solid ground to tighten the simulation iterations to more realistic values. With this data, it was also possible to calculate the value of an important input parameter, HETP, that was to be used in the simulator. After successfully profiling the operation method of the single staged discontinuous columns, stage two of the present work began: Process modelling and packing usage simulation while comparing the results in the software Aspen Plus®. By using every collected data so far and converging the modelling results, using the following iterative calculations, to a realistic scenario, it was possible to conclude about the viability study. Since the packing section is too small and the inevitable increased pressure drop, caused by the usage of the packing, data showed that, for optimal volumetric flow rate, there was flooding occurrence. Trying to manoeuvre the problem, lower volumetric flow rates were tested as well but, due to improper equilibrium between the vaporization rate and the volumetric feeding rate, the column dried up. For lower volumetric flow rates, there is a greater amount of vaporization occurrence when comparing to the volumetric feeding rate. By means of simulation and modelling, it was shown that the usage of a packing bed on the single stages discontinuous columns is unreliable. Additional calculations were made to allow an estimation of a minimum acceptable diameter that would not flood the column at various volumetric flow rates. The values were presented as suggestions for future modifications if needed

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 (&gt; 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<br>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 (&gt; 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

Submitted by Jesiel Ferreira Gomes (jesielgomes@ufcg.edu.br) on 2018-04-20T20:53:07Z No. of bitstreams: 1 SHIRLENE KELLY SANTOS CARMO – TESE (PPGEQ) 2015.pdf: 3441674 bytes, checksum: 2a66c0c04d01e56f10189d8b206ebc1c (MD5)<br>Made available in DSpace on 2018-04-20T20:53:07Z (GMT). No. of bitstreams: 1 SHIRLENE KELLY SANTOS CARMO – TESE (PPGEQ) 2015.pdf: 3441674 bytes, checksum: 2a66c0c04d01e56f10189d8b206ebc1c (MD5) Previous issue date: 2015-02-06<br>Capes<br>Grande parte das indústrias apresenta complexidade no que diz respeito ao seu modo de operação. A fim de reduzir os problemas relacionados ao forte acoplamento existente nesses processos, a busca pela incorporação de dispositivos de inteligência artificial vem apresentando uma tendência crescente nos últimos anos. Devido à complexidade de operação e controle em processos multivariáveis, o diagnóstico e monitoramento de falhas nos processos tornaram-se cada vez mais difícil, com isso a aplicação destes dispositivos tem alcançado resultados satisfatórios em relação aos procedimentos executados com operadores humanos. A análise de componentes independentes (ICA) é uma técnica de separação de sinais que se baseia no uso de estatísticas de ordem superior para estimar cada uma das fontes desconhecidas por meio da observação de diversas misturas geradas a partir destas fontes. Embora sejam encontrados trabalhos recentes sobre a utilização do ICA em processos industriais, apenas dois trabalhos até o presente momento, foram aplicados em processos envolvendo colunas de destilação. O presente trabalho tem como objetivo propor uma estratégia de controle a uma coluna de destilação de alta pureza. A estratégia é baseada na técnica de separação de sinais ICA, tornando as malhas de controle desacopladas e facilitando assim o desempenho do controle. O desempenho do sistema de controle utilizando a técnica apresentou excelentes resultados em relação a uma estrutura convencional sem desacoplamento. As estruturas de controle foram implementadas em ambiente Aspen Plus DynamicsTM e Simulink/ Matlab®. O processo foi estruturado em ambiente Aspen Plus Dynamics™ e os controladores foram implementados no Simulink.<br>Much of the industry presents complexity with regard to its mode of operation. In order to reduce the problems related to existing strong engagement in these processes, the search for the incorporation of artificial intelligence devices has shown an increasing trend in recent years. Due to the complexity of operation and control in multivariate processes, the diagnosis and fault monitoring in the processes have become increasingly difficult, thus the application of these devices has achieved satisfactory results in relation to procedures performed with human operators. The independent component analysis (ICA) is a signal separation technique that is based on the use of higher order statistics to estimate each of the unknown source by observing various mixtures generated from these sources. Although found recent work on the use of the ICA in industrial processes, only two studies to date, have been applied in cases involving distillation columns. This paper aims to propose a control strategy to a high purity distillation column. The strategy is based on the ICA signal separation technique, making decoupled control loops, thus facilitating control performance. The performance of the control system using the technique showed excellent results compared to a conventional structure without decoupling. The control structures have been implemented in Aspen Plus Dynamics™ and Simulink / Matlab® environment. The process was structured environment Aspen Plus Dynamics™ and the controls were implemented in Simulink.

Mestrado em Engenharia Química<br>A EGEO Solventes S.A, empresa cuja atividade se dedica à regeneração de solventes orgânicos industriais usados, tem por objetivo a contínua melhoria e otimização da sua unidade fabril, em particular as suas operações de destilação. Esta dissertação insere-se neste âmbito. Numa primeira fase fez-se o diagnóstico de funcionamento da coluna de enchimento e identificaram-se problemas associados ao equipamento auxiliar e refinou-se o procedimento de arranque. Caudalímetros, válvula de refluxo, sondas de nível, válvula de vapor e sensor de temperatura foram elementos sujeitos a intervenções ou propostas de melhoria. Numa segunda fase do trabalho, simularam-se em Aspen Plus® destilações conduzidas na coluna de enchimento da empresa. Para tal, foram realizados três ensaios que consistiram no fracionamento das misturas solventes designadas por “Ecosolve Met” para os dois primeiros e "Ecosolve 07C" para o terceiro. Foram monitorizadas e registadas as respetivas temperaturas, caudais e composições ao longo do tempo. Foi feita a configuração do bloco BatchSep® do Aspen Plus®, correram-se as simulações e mostrou-se, por comparação com os resultados experimentais da unidade, que as previsões fornecidas são representativas, particularmente no caso da mistura “Ecosolve Met”. Dos ensaios realizados e das simulações computacionais efetuadas confirmou-se a importância de iniciar a destilação a refluxo total e avançar depois para a operação em semi-contínuo. A composição máxima do destilado depende significativamente de se conduzir a destilação a refluxo constante ou a refluxo variável, mas em qualquer caso as simulações em Aspen Plus® mostraram ser uma boa ferramenta de estudo e previsão.<br>EGEO Solventes S.A., a company whose main activity focuses on solvent regeneration of used industrial organic solvents, intends on giving continuity to its constant improvement and on the optimization of its factory unit, in particular its distillation operations. The work now presented is developed in this sense. In an initial phase, a diagnosis was performed to the packed column and some limitations were identified associated to the auxiliary equipment and the starting procedure was refined. The flowmeters, the reflux valve, the level sensors, the steam valve and the temperature sensor were the equipment subjected to interventions or improvement proposals. In a second phase of the work presented, simulations were performed in Aspen Plus® of distillations conducted in the packed column of the company. To do so, three tests were performed which consisted in the fractioning of the mixtures designated by “Ecosolve Met”, for the first two and “Ecosolve 07C” for the third. The respective temperatures were monitored and registered, as well as the flows and compositions over time. The Aspen’s block, BatchSep® was configurated, the simulations were performed and it was shown, by comparison with the experimental results of the unit, that the previsions provided are representative, particularly in the case of the mixture “Ecosolve Met”. The tests and computational simulations performed allowed to conclude the importance of starting the distillation in total reflux and advancing then to the operation in semicontinuous. The maximum composition of the distillate depends significantly on conducting the distillation in constant reflux or variable reflux, but in any case the simulations with Aspen Plus® have shown to be a good study and prediction tool.

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.

Ce travail de recherche porte sur la modélisation mathématique des principaux procédés sidérurgiques en suivant une approche systémique. L’objectif est d’élaborer un outil de modélisation de l’ensemble de la filière destiné à l’optimiser du point de vue énergétique et environnemental. Nous avons développé des modèles physico-chimiques du haut fourneau, de la cokerie, de l’agglomération et du convertisseur. Ces modèles ont ensuite été reliés entre eux sous forme d’un diagramme de flux unique en utilisant le logiciel ASPEN Plus. Dans une première partie, nous nous sommes particulièrement intéressés au haut fourneau à recyclage, une variante innovante du haut fourneau dans laquelle les gaz de gueulard sont recyclés et réinjectés aux tuyères après capture du CO2. Nous avons testé une réinjection à un niveau (aux tuyères) et à deux niveaux (tuyères et ventre). Les résultats ont été comparés avec succès à des données expérimentales issues d’un réacteur pilote et montrent que le recyclage permet une baisse de plus de 20 % des émissions de CO2 du haut fourneau. Le recyclage à deux niveaux ne semble pas plus performant que celui à un seul niveau. Dans un deuxième temps, nous avons simulé le fonctionnement d’une usine sidérurgique intégrée dans son ensemble. Différentes configurations ont été testées, pour un haut fourneau classique ou un haut fourneau à recyclage, en considérant un éventuel recyclage du laitier de convertisseur à l’agglomération, et en étudiant l’influence de la teneur en silicium de la fonte sur toute la filière. On montre notamment qu’il est possible de réduire le prix de revient de la tonne d’acier en substituant et recyclant différents sous-produits<br>This research study deals with mathematical modeling of the main steelmaking processes following a systems approach. The objective was to build a modeling tool of the whole steelmaking route devoted to its energetic and environmental optimization. We developed physical-chemical models for the blast furnace, the coke oven, the sintering plant and the basic oxygen furnace. These models were then linked together in a single flow sheet using the ASPEN Plus software. First, we focused on the top gas recycling blast furnace, a novel variant of the blast furnace in which the top gas is recycled and re-injected into the tuyeres after CO2 removal and capture. We tested both a reinjection at one level (tuyeres only) and at two levels (tuyeres and shaft). The results were successfully compared with experimental data from a pilot reactor and demonstrate that recycling can lower the blast furnace CO2 emissions by more than 20%. Recycling at two levels does not seem more efficient than at a single level. Second, we simulated the operation of an entire integrated steelmaking plant. Different configurations were tested, using a conventional blast furnace or a top gas recycling blast furnace, considering a possible recycling of the converter slag to the sintering plant, and studying the influence of Si content in the hot metal on the entire steelmaking plant operation. We show that it is possible to reduce the cost of producing steel by substituting and recycling various by-products

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<br>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

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 ». <p>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.<p>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.<p><p>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 ».<p>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. <p>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.<p><br>Doctorat en Sciences de l'ingénieur<br>info:eu-repo/semantics/nonPublished

The work deals with optimization of the process of production of cumene from benzene by its alkylation with propylene. This process also involves an undesirable reaction between cumene and propylene to form p-diisopropylbenzene (PIDB). Since the activation energy of the second reaction is higher than the first one, lower reactor temperature is favored to improve the selectivity of the reaction towards cumene. This can be done by increasing the reactor size, finding a suitable method of distillation and designing the distillation columns accordingly. All the variations increase the capital and/or energy cost but also decrease the amount of raw material required. Thus this provides a classic example of an engineering design and optimization of a process. The process present in the design book by Turton et. al is referred and consists of a tubular reactor and two distillation columns. The purpose of this project is to develop an optimum design for the cumene plant which is aimed at saving maximum amount of raw material possible and also reduce the costs to an extent.

Air is a mixture of various gases. Each of these gases have got some kind of uses. As such, separation of air into its constituent gases becomes very necessary from commercial point of view. For separation of air into its constituent gases, it is necessary to liquefy the same. In this project, simulation of liquefaction of air, followed by its separation was done using Aspen Plus simulating tool. The model under consideration was Linde single-column system. Also, the effect of various process conditions on the yield and purity of final product were analyzed. It was found that by using Linde single-column system, oxygen of almost 98-99% purity could be obtained. However, the purity of nitrogen obtained was only about 90%.