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

No description available.

The following chapters deal with the chemistry, catalytic poisoning, newer catalyst technologies, and possible future solutions to increase the efficiency of creating high-value products by thermochemically converting gasified biomass (producer gas). Chapter 1 puts emphasis on multifunctional catalysts containing transition metals that are used for renewable fuel production. High-value products such as gasoline-range hydrocarbons, dimethyl ether (DME), aldehydes, isobutane, isobutene and other olefins can be produced with gasified biomass due to the gas containing syngas (H2 + CO). The chemistry and production of these chemicals is discussed in the review. Chapter 2 describes the reactor design of a bench scale system and results after using a Mo/HZSM- 5 catalyst for aromatic hydrocarbon creation. This chapter also discusses issues that came with trying to control the temperature without any reactor intercooling. Chapter 3 shows the feasibility of using a particular multifunctional catalyst with a lab scale system and also shows the importance of certain process variables including temperature, space velocity, gas ratios, and pressure. The subject of the importance of the cleanliness of the producer gas is also discussed so that maximum high-value product yield can be achieved with the greatest efficiency. Chapter 4 discusses the implementation of a bench scale and pilot scale reactor design (both with intercooling) and the results of scale-up when using the catalyst mentioned in Chapter 3. Chapter 5 involves the modelling of an industrialized system with Aspen Plus. The economics of industrial plants to produce hydrocarbons from coal or wood feedstocks at scales of 5, 50 and 5000 tons per day were modeled using CAPCOST.

Due to the remote and dispersed nature of Alberta’s oil wells, it is not economical for the energy industry to capture all of the solution gas produced and as a result, the gas is being flared and vented in significant amounts. The objective of this research is to aid in the conversion of solution gas into dimethyl ether (DME) in a remote location by designing a distillation column that purifies DME and its reaction by-products, carbon dioxide, methanol and water. In order to develop an implementable solution, the distillation equipment must fit inside of a 40-foot shipping container to be transported to remote locations. Given the size constraint of the system, process intensification is the best strategy to efficiently separate the mixture. Several process intensification distillation techniques are explored, including semicontinuous distillation, the dividing wall column (DWC) and a novel semicontinuous dividing wall column (S-DWC). The traditional semicontinuous distillation column purifies DME to fuel grade purity, however the other components are not separated to a high enough grade given the height constrain of the system. The DWC and S-DWC both purify DME to its desired purity along with producing high purity waste streams. The S-DWC purifies the reaction intermediate methanol to a grade slightly higher than the DWC and is pure enough to recycle back to the reactor. An economic comparison is made between the three systems. While the DWC is a cheaper method of producing DME, the trade-off is the purity of the methanol produced. Overall, this research shows that it is possible to purify DME and its reaction by-products in a 40-foot distillation column at a cost that is competitive with Diesel. / Thesis / Master of Applied Science (MASc)

Organic esters are an important class of industrial and commercial chemicals that can be found in solvents, plasticizer, food flavours, detergents, agrochemicals, and pharmaceuticals. The most common way to synthesis organic esters is with esterification or transesterification. Where esterification was the chosen method in this thesis.  This thesis provides a techno-economic assessment on the production of propyl acetate and glycerol trivalerate through different continuous routes that is than compared with batch production under the same conditions. Simulations was done on trivalerate due to limited literature and data on pentaerythritol tetravalerate. Different continuous technologies that have been assessed in this thesis was plug flow reactor (PFR), Reactive Distillation (RD), and Reactive – Extractive Distillation (RED). The production of mono- and polyol esters with different unit operators was simulated in Aspen Plus V.14. Techno-Economic analysis was conducted with APEA (Aspen Process Economic Analyzer), where cost of raw materials, products, and utilities was inserted to evaluate annual operating cost and product sale. Reaction kinetic for esterification of trivalerate was estimated by obtained values from simulations of a Gibbs reactor in Aspen Plus at four different temperatures. Kinetics was estimated by applying the relation between the chemical equilibrium constant and the Arrhenius equation. Where rate constant and activation energy for forward and revers reaction was obtained by varying min and max values for lsqcurvefit in MATLAB and then validate results with published kinetics.  Results from production of propyl acetate with batch, PFR and RED provides an annual profit of approximately 1 M$ at a capacity of 41.65 kton/year. The three different process provides also approximately an equal capital cost, operating cost, equipment cost, and installed cost according to APEA. RED provided the lowest propyl acetate yield at 93%, batch and PFR provided a propyl acetate yield of 94%.  Results from production of trivalerate with batch, PFR, and RD provides an annual profit of 5.4, 5.78, and 9.2 M$ at a capacity of approximately 5 kton/year. Where RD process provides the lowest capital cost, operating cost, equipment cost, and installed cost compared to batch and PFR processes according to APEA. Obtained results from production of trivalerate can be used to evaluate the economic and technical feasibility of a continuous production plant for pentaerythritol tetravalerate (PETV). Where initial simulations show a good economic and technical viability of a continuous ester production plant.

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