This work includes wetted wall column experiments that measure the CO₂ equilibrium partial pressure and liquid film mass transfer coefficient (kg') in 7, 9, 11, and 13 m MEA and 2, 5, 8, and 12 m PZ solutions. A 7 m MEA/2 m PZ blend was also examined. Absorption and desorption experiments were performed at 40, 60, 80, and 100°C over a range of CO₂ loading. Diaphragm diffusion cell experiments were performed with CO₂ loaded MEA and PZ solutions to characterize diffusion behavior. All experimental results have been compared to available literature data and match well. MEA and PZ spreadsheet models were created to explain observed rate behavior using the wetted wall column rate data and available literature data. The resulting liquid film mass transfer coefficient expressions use termolecular (base catalysis) kinetics and activity-based rate expressions. The kg' expressions accurately represent rate behavior over the very wide range of experimental conditions. The models fully explain rate effects with changes in amine concentration, temperature, and CO₂ loading. These models allow for rate behavior to be predicted at any set of conditions as long as the parameters in the kg' expressions can be accurately estimated. An Aspen Plus® RateSep™ model for MEA was created to model CO₂ flux in the wetted wall column. The model accurately calculated CO₂ flux over the wide range of experimental conditions but included a systematic error with MEA concentration. The systematic error resulted from an inability to represent the activity coefficient of MEA properly. Due to this limitation, the RateSep™ model will be most accurate when finetuned to one specific amine concentration. This Aspen Plus® RateSep™ model allows for scale up to industrial conditions to examine absorber or stripper performance. / text

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.

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.

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.

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

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.

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.

Thermodynamics is important for the design of amine scrubbing CO₂ capture processes. CO₂ solubility and amine volatility in aqueous amines were measured at high temperature and pressure. A rigorous thermodynamic model was developed for MEA-CO₂-H₂O in Aspen Plus®. CO₂ solubility at 80-190°C was obtained from total pressure measurements. Empirical models as a function of temperature and loading were developed for CO₂ solubility from 40 to 160°C in aqueous monoethanolamine (MEA), piperazine (PZ), 1-methylpiperazine (1MPZ), 2-methylpiperazine (2MPZ), PZ/2MPZ, diglycolamine® (DGA®), PZ/1MPZ/1,4-dimethylpiperazine (1,4-DMPZ), and PZ/methyldiethanolamine (MDEA). The high temperature CO₂ solubility data for MEA is comparable to literature and compatible with previous low temperature data. For MEA and PZ, amine concentration does not have obvious effects on the CO₂ solubility. The heat of CO₂ absorption derived from these models varies from 66 kJ/mol for 4 m (molal) PZ/4 m 2MPZ and to 72, 72, and 73 kJ/mol for MEA, 7 m MDEA/2 m PZ, and DGA. The heat of absorption estimated from the total pressure data does not vary significantly with temperature. At 0-0.5 loading ([alpha]), 313-413 K, 3.5-11 m MEA (mol fraction x is 0.059-0.165), the empirical model of MEA volatility is ln(PMEA/xMEA) = 30.0-8153/T-2594[alpha]²/T. In 7 m MEA with 0.2 and 0.5 loading, PMEA is 920 and 230 Pa at 120°C. At 0.3-0.5 loading, the enthalpy of MEA vaporization, -[Delta]Hvap,MEA, is about 70-73 kJ/mol MEA. At 0.25-0.4 loading, 313-423 K, 4.7-11.3 m PZ (x is 0.078-0.169), the empirical model of PZ volatility is ln(PPZ/xPZ) = -123+21.6lnT+20.2[alpha]-18174[alpha]²/T. In 8 m PZ with 0.3 and 0.4 loading, PPZ is 400 and 120 Pa at 120°C, and 2620 and 980 Pa at 150°C. At 0.25-0.4 loading, -[Delta]Hvap,PZ is about 85-100 kJ/mol PZ at 150°C and 66-80 kJ/mol PZ at 40°C. [Delta]Hvap,PZ has a larger dependence on CO₂ loading than [Delta]Hvap,MEA in rich solution because of the more complex speciation/reactions in PZ at rich loading. Specific heat capacity of 8 m PZ is 3.43-3.81 J/(g•K) at 70-150°C. Two new thermodynamic models of MEA-CO₂-H₂O were developed in Aspen Plus® starting with the Hilliard (2008) MEA model. One (Model B) includes a new species MEACOOH and it gets a better prediction than the other (Model A) for CO₂ solubility, MEA volatility, heat of absorption, and other thermodynamic results. The Model B prediction matches the experimental pKa of MEACOOH, and the measured concentration of MEACOO-/MEACOOH by NMR. In the prediction the concentration of MEACOOH is 0.1-3% in 7 m MEA at high temperature or high loading, where the heat of formation of MEACOOH has effects on PCO₂ and CO₂ heat of absorption. Model B solved the problems of Model A by adding MEACOOH and matched the experimental data of pKa and speciation, therefore MEACOOH may be considered an important species at high temperature or high loading. Although mostly developed from 7 m MEA data, Model B also gives a good profile for 11 m (40 wt%) MEA. / text

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) / 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 / Capes / 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. / 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.

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