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Chemical looping combustion (CLC) is a promising fossil fuel combustion technology, which is able to separate CO2 from the flue gases without a large consumption of energy. In this thesis, the study was extended to look at the use of chemical looping materials within traditional fluidised bed combustion and investigation of the interaction between the fuel, the supplied air and the chemical looping agent. Three topics of chemical looping combustion are discussed, including 1) the Sherwood number in the fluidised bed; 2) properties of different oxygen carriers, Fe2O3 and CuO (with supporting materials), were tested in the fluidised bed reactor; 3) the simulation of a steady state and a dynamic model of a coal-fired CLC power plant using Fe2O3 as oxygen carriers. The Sherwood number, which represents the mass transfer rate, is important in the calculation of CLC process. With Sherwood number, the mass transfer rate kg around the acting particle can be calculated using correlation Sh=kg∙d/D, where d is the diameter of acting particle, and D is the diffusivity around the acting particle. Hayhurst and Parmar (Hayhurst and Parmar 2002) calculated the Sherwood number in the fluidised bed by using the CO/CO2 ratio, which was measured by the temperature difference between the carbon particle and the bulk phase (Hayhurst and Parmar 1998). However, the temperature of the particle could be overestimated, so the CO/CO2 ratio could be underestimated. In this thesis, a universal exhaust gas oxygen (UEGO) sensor was employed, which could measure the actual carbon consumption rate in the fluidised bed by oxidizing CO in the sample gas into CO2 and. Fe particles of the same size of the char particle is used to measure the O2 consumption rate, and thus eliminate uncertainty in the Sherwood number. The CO/CO2 ratio was calculated by using the carbon consumption rate and the O2 consumption rate. In contrast to Hayhurst and Parmar (Hayhurst and Parmar 2002) who assumed CO2 was the main product, for this char the actual ratio of CO/CO2 was almost zero. The measurement here is in agreement with Arthur. This more accurate determination of CO/CO2 allows a better estimate of the mass transfer coefficient and leads to a correction of the Hayhurst and Parmar’s (Hayhurst and Parmar 2002) correlation by a factor of 1⁄2. Interestingly, very small fluidised beds have mass transfer coefficients which are about twice that expected in a large bed (owing to the very different flow and indeterminate flow pattern). This means the correlation of Hayhurst and Parmar (Hayhurst and Parmar 2002), by fortuitous coincidence works wells for beds with diameters < 30 mm., without the correction factor, should be ignored. In the fluidised bed in a typical CLC process, different fluidising material could have different influence on the reactions. Thus, it is worth discussing different kinds of fluidising materials. The char combustion in the fluidised bed was simulated by using inert (sand) and active (Fe2O3 or CuO) fluidising materials, and air as fluidising gas. The results indicated that 1) CO combustion in the boundary layer leads to smaller carbon consumption rate and larger oxygen consumption rate; 2) Using Fe2O3 particles as fluidising materials slows down the carbon consumption rate, since the diffusivity of CO2 is smaller than CO; 3) CuO particles slow down the carbon consumption rate at large Sherwood number (Sh=2 or 2.5). The influence of using CuO as fluidising material is further discussed experimentally by using low O2 fluidising gas. The results indicated that since the amount of CuO used in the experiment is small, when the O2 concentration in the bulk phase is lower than the equilibrium concentration, the O2 concentration in the bulk phase gradually decreases, and the O2 concentration in the bulk phase has large influence on the char particle combustion. A steady state model of a coal-fired CLC power plant was simulated. The aim of the model was to test the suitable operating conditions of the power plant, such as recycle rate of oxygen carriers, for the power plant design. In the steady state model, the power plant consists of a combustor and a steam cycle. Hambach lignite coal, Polish bituminous coal and natural gas were tested as fuels. The results indicated that: (1) The effect of the fuel is largely due to the amount of oxygen required per GJ released; (2) Preheating is important, but seems to have a minor effect since the most of the heat is released at temperatures well above the pinch point; (3) since the temperatures of heat source in this research is well above the pinch point, all heat are usable for the steam cycle. In this case, the steam cycle and the chemical looping plant could be optimised separately; (4) As long as the preheat temperature of the air flow into the air reactor is higher than the temperature of turbines, in most of cases the power output is unaffected by the choice of variables, leaving the designer free to choose the most convenient. With the conclusions above, a dynamic model of a coal-fired CLC power plant using Fe2O3 as oxygen carrier is then simulated. The aims of this simulation include: 1) explaining the kinetics of Fe2O3 oxygen carriers at high temperature (1223K) in a fluidised bed reactor using Brown’s data (Brown 2010); 2) a 1GWth dynamic power plant was simulated to test different cases including changing power supply and power storage. In the dynamic model, a chemical looping power plant using Hambach lignite char is tested, and the parameters of the system are adjusted so as to simulate the operations of a real chemical looping power plant. The two-phase model is employed for the fluidised bed reactors. Experimental data from Brown (Brown 2010) was simulated using this model first to test its validity. Then the model is scaled up to simulate a 1GWth dynamic power plant. The ideal operation conditions are found, and a char stripper is found helpful for carbon capture.

Orientadores: Maria Regina Wolf Maciel, Henry França Meier, Antonio Andre Chivanga Barros / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-03T15:25:11Z (GMT). No. of bitstreams: 1 Wiggers_VinicyusRodolfo_M.pdf: 4312543 bytes, checksum: c9c8ccdabb1190ba49ffe38d966b7226 (MD5) Previous issue date: 2003 / Resumo: A pirólise, uma das muitas alternativas de processos de conversão química de resíduos sólidos, tem recebido uma atenção especial de ambientalistas, engenheiros e da comunidade científica. Este processo tem sido testado em um número incontável de plantas piloto, e muitos sistemas em escala industrial já são operados com sucesso. Sofrendo aquecimento em uma atmosfera livre de oxigênio, muitas substâncias orgânicas de cadeia longa, podem ser fracionadas via craqueamento térmico e reações de condensação, em frações gasosas, líquidas e sólidas de menor peso molecular com maior valor econômico. Ao contrário da incineração que é altamente exotérmica, a pirólise é endotérmica, ocorre numa faixa de temperatura da ordem de 300 a 600°C e apresenta vantagens como a menor formação de dioxinas e a possibilidade de processo autotérmico. Este trabalho tem o propósito de simular, projetar e construir uma planta piloto de pirólise em reator de leito móvel através de solução de modelos matemáticos e métodos numéricos. Além disso, pretende-se desenvolver uma estratégia do tipo problema inverso para ajuste numérico de parâmetros térmicos e cinéticos do processo. Para tanto, projetou-se e montou-se um aparato experimental em escala piloto, com finalidade multi-propósito, para aquisição de dados do processo com e sem reação, mediante o desenvolvimento e uso do modelo microscópico unidimensional e permanente de conservação da massa e da energia / Abstract: Pyrolysis, one of many solid waste chemical conversion processes, has been receiving a special atenttion from engineers, researches and environment specialists. The pyrolysis has been tested in many pilot plants, and some industrial plants are operated with success. Heating in a controled atmosphere absenced of oxygen, an organic portion of waste materials can be converted into mixture gases, oils with lower molecular weight and others products with higher economic value. This trasnformation occurs through thermal cracking and condensation reaction. Whereas incineration is exothermic, pyrolysis is endothermic and runs in range temperatures from 300 to 600°C. This process still presents some advantages like smaller dioxines formation than the incineration and also the possibility of autothermal operation of the process This work has the propose to simulate, project and build a pilot plant of pyrolysis with a fluidised bed reactor, by using mathematical modelling and numerical methods for simulation of the process It also intends to develop strategies to solve an inverse problem to predict thermal and kinetics parameters of the model from experimental data obtaneid in a pilot plant and a metodology to determine a thermic and kinetic parameters of solid waste. To get this objective, a microscopic model l-D and steady state, of mass and energy conservation was developed, the simulation for design and the construction of an experimental aparatus in a pilot plant scale was realized, to get a process data with and without reaction, to intend a scale-up from process / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

No / Oxidative coupling of methane (OCM) is suggested to be a promising process for the conversion of the abundant natural gas into useful chemicals. However, this reaction faces many drawbacks such as low yields for higher hydrocarbons, fast catalyst deactivation, and huge heat effects of the reaction. Only a well-designed fluidized bed reactor is able to overcome effectively those disadvantages and to provide a satisfactory continuous operation. However, design approaches for fluidized bed reactors are still based on models developed during 70s and 80s, which cannot take into account various hydrodynamic effects on the reactor performance. Thus, a reactor designer has usually to rely on extensive experiments in order to improve the classical fluidized bed reactor design. In this work, the relevance of hydrodynamics, reactor geometry, and feeding policy on the performance of a fluidized bed reactor for the OCM is shown. For this purpose, several case studies of fluidized bed reactors are simulated in full 3D geometry under the same reaction conditions, but with different reactor geometries and feeding policy. These studies show the significance of hydrodynamic parameters for the reactor performance, and moreover, how fluidized bed reactor performance can be improved by a careful study of coupled momentum-mass transport-reaction phenomena. Furthermore, it can be demonstrated that a suitable distributed feeding policy of oxygen provides an improved yield while a traditional fluidized bed reactor design results in an inferior performance among all investigated cases.