The control of particle emissions from an oil refinery is often difficult, due to changing operational conditions and the limited range of available treatment options. Excessive particle emissions have often been attributed start up problems with Fluidized Catalytic Cracker Units (FCCU) and little information is available regarding the exact composition and nature of these excessive emissions. Due to the complex nature of a FCCU, it has in the past been difficult to identify and control emissions, without the use of expensive end of pipe technologies. An Australian Oil Refinery, concerned with their catalyst emissions, sponsored this study of FCCU particle emissions. Due to the industrial nature of the project, a holistic approach to the management of emissions was taken, instead of a detailed investigation of a single issue. By looking at the broader range of issues, practical and useful outcomes can be achieved for the refinery. Initially, detailed emissions samplings were conducted to investigate the degree of particle emissions under start up conditions. Stack emissions were collected during a standard start up, and analysed to determine the particle size distribution and metal concentration of the emitted material. Three distinct stages of emissions were discovered, initially a high concentration of larger particles, followed by a peak in the very fine particles and finally a reduction of particle emissions to a more steady or normal operational state. The variation in particle emissions was caused by operational conditions, hardware design and catalyst characteristics. Fluctuations in the gas velocity through the system altered the ability of the cyclones to collect catalyst material. Also, the low bed level allowed air bypass to occur more readily, contributing to the increased emissions levels seen during the initial stage of the start up. Reduced fluidity characteristics of the circulating catalyst also affected the diplegs operations, altering the collection efficiency of the cyclone. During the loading of catalyst into the system, abraded material was quickly lost due to its particle size, contributing to fine particle emissions levels. More importantly, thermal fracturing of catalyst particles occurred when the cold catalyst was fed into the hot regenerator. Catalyst particles split causing the generation of large amounts of fine particle material, which is easily lost from the system. This loading of catalyst directly linked to the period of high concentration of fine particles in the emissions stream. It was found that metals, and in particular iron, calcium and silicon form a thick layer on the outside of the catalyst, with large irregular shaped metal ridges, forming along the surface of the particle. These ridges reduce the fluidity of the catalyst, leading to potential disruptions in the regenerator. In addition to this, the metal rich ridges are preferentially removed via attrition, causing metal rich material to be emitted into the atmosphere. To overcome these high particle emissions rates from the FCCU the refinery should only use calcinated catalyst to reduce the influence of thermal process and particle fracture and generation. Although the calcinated catalyst can fracture when added to the system, it is far less than that obtained with uncalicinated catalyst. To further reduce the risk of particle fracture due to thermal stresses the refinery should consider reducing the temperature gradients between the hot and cold catalyst. Due to the economics involved with the regenerator, possible pre-warming of catalyst before addition into system is the preferred option. This pre-heating of catalyst should also incorporate a controlled attrition stage to help remove the build up of metals on the surface of the particles whilst allowing this material to be collected before it can be released into the atmosphere. The remove of the metal crust will also improve the fluidity of the system and reduce the chance of catalyst blockages occurring. Finally, modelling of the system has shown that control of key parameters such as particle size and gas velocity are essential to the management of air emissions. The refinery should look at adjusting start up procedures to remove fluctuations in these key parameters. Also the refinery should be careful in using correlation found in the literature to predicted operational conditions in the system as these correlations are misleading when used under industrial situations.

M. Tech. Engineering Chemical. / Aims to investigate how the addition of impurities in a CO2 stream affects the adsorption capacity of CO2 on South African coals. To achieve this aim, the following objectives were carried out. 1. To measure the adsorption isotherms and adsorption capacities of pure CO2 and flue gas mixtures on various South African coals under in-seam conditions including pressures up to 88 bar and isothermal temperature of 35 &#x00BA%x;C; 2. To evaluate the effects of coal rank on the adsorption isotherms and adsorption capacities of pure CO2 and flue gas mixtures; 3. To do a comparative study to evaluate the effects of CO2 impurities on the adsorption capacity of pure CO2 on coal; 4. To study the degree of preferential sorption of the individual flue gas mixtures components on coal; 5. To determine the suitability of the Langmuir, Freundlich, and Temkin adsorption isotherm models in representing pure CO2 adsorption onto coal; and 6. To determine the suitability of Extended Langmuir (EL) adsorption models in representing the flue gas mixture adsorption onto coal.

Submitted by Luciana Sebin (lusebin@ufscar.br) on 2016-10-11T18:25:57Z No. of bitstreams: 1 DissECC.pdf: 1201673 bytes, checksum: c96ddf2834cfea8ddcc495673a274880 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2016-10-17T13:18:16Z (GMT) No. of bitstreams: 1 DissECC.pdf: 1201673 bytes, checksum: c96ddf2834cfea8ddcc495673a274880 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2016-10-17T13:18:26Z (GMT) No. of bitstreams: 1 DissECC.pdf: 1201673 bytes, checksum: c96ddf2834cfea8ddcc495673a274880 (MD5) / Made available in DSpace on 2016-10-17T13:23:54Z (GMT). No. of bitstreams: 1 DissECC.pdf: 1201673 bytes, checksum: c96ddf2834cfea8ddcc495673a274880 (MD5) Previous issue date: 2016-03-14 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / The cement industry, closely associated with the global warming question, accounts for significant emissions of CO2 and other air pollutants, such as SO2 and NO2 in the atmosphere. In search for ways to mitigate the atmospheric CO2, we performed semicontinuous cultures of Chlorella sorokiniana under phototrophic conditions to test the effect of a flue gas simulation (18% CO2, 9% O2, 300 ppm NO2 and 140 ppm SO2). This was provided once a day in six serial experiments, in which the exposure to the gas was increased through the increase of bubbling time. A constant flow rate allowed us to calculate the total volume of gas introduced into the system each day (0.1, 0.3, 0.8, 1.5, 6 and 48 L). Air-CO2 (18%) was used as control and its bubbling time was pHregulated. Culture medium acidification led to suboptimal growth conditions that affected cell density, photosynthetic activity, cell viability and the biochemical composition of C. sorokiniana. Compared to control, the specific growth rate decreased by 17 and 3,9% in cultures that received 6 and 48 L gas d-1, respectively. The pulseamplitude modulated (PAM) fluorometry was used for culture evaluation. It revealed low maximum quantum yield (ΦM 0.40) and operational quantum yield (Φ'M 0.47) values one day after 48 L gas bubbling. Light saturation curves confirmed the negative effects of long-time gas simulation stress. On the other hand, quenching analysis indicated an increase in photochemical light use and low values of non hotochemical quanching (qN and NPQ). Exposure of the cells to the flue gas simulation resulted in lower cell viability compared to control. Biochemical analysis showed that 6 and 48 L gas d-1 significantly increased protein content by 75% and 154%, respectively; total carbohydrates also increased in the presence of the gas, 148% and 195%, respectively. Despite the physiological changes, C. sorokiniana resisted suboptimal growth conditions imposed by the gas, supporting its vigorous nature and relevance in biotechnological aplications with flue gases. / Inserida na problemática do aquecimento global, a indústria de cimento é uma das que mais contribui para emissão de CO2 e de poluentes como SO2 e NO2 na atmosfera. Visando alternativas para mitigação desses gases, que são oriundos principalmente de processos de combustão, foram testados seis cultivos fototróficos semicontínuos de Chlorella sorokiniana, para avaliar o efeito de diferentes volumes (0,1; 0,3; 0,8; 1,5; 6 e 48 L d-1) de uma simulação gasosa composta por CO2 (18%), O2 (9%), NO2 (300 ppm) e SO2 (140 ppm). Os volumes variaram conforme o aumento do tempo de borbulhamento diário dos gases nos cultivos. O tratamento controle, composto por ar sintético e CO2 (18%), teve seu tempo de borbulhamento definido pela variacão de pH do meio. O fornecimento da simulação gasosa resultou na acidificação do meio de cultura e afetou a densidade celular, a atividade fotossintética, a viabilidade celular e a composição bioquímica de C. sorokiniana. Comparadas ao controle, as exposições diárias de 6 e 48 L gás d-1 reduziram a taxa específica de crescimento em 17 e 39%, respectivamente. Por meio da fluorescência de amplitude modulada (PAM), verificamos baixos valores de rendimento quântico máximo (ΦM 0,40) e operacional (Φ’M 0,47) um dia após o primeiro borbulhamento de 48 L gás. Curvas de saturação de luz confirmaram os efeitos negativos do estresse prolongado à mistura gasosa. A análise de decaimento da fluorescência da clorofila, por sua vez, indicou um aumento da energia luminosa direcionada à fotoquímica da fotossíntese (qP) e baixos valores de dissipação não fotoquímica da energia luminosa (qN e NPQ). A simulação gasosa resultou, ainda, em menor viabilidade celular, se comparada ao controle. Pelas análises bioquímicas, constatamos que 6 e 48 L gás d-1 levaram a um aumento significativo do conteúdo proteico de 75% e 154%, respectivamente; os mesmos tratamentos também aumentaram a quantidade de carboidratos totais em 148% e 195%. Apesar das alterações fisiológicas, C. sorokiniana resistiu às condições subótimas de crescimento, o que comprova sua robustez e relevância em aplicações biotecnológicas envolvendo gases de combustão.

Orientador: Arai Augusta Bernardez Pecora / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-13T23:51:53Z (GMT). No. of bitstreams: 1 Morita_EugeniodeSouza_M.pdf: 4021816 bytes, checksum: da9670c797e58d9f79ea109135e7df7d (MD5) Previous issue date: 2009 / Resumo: O objetivo deste trabalho é avaliar as emissões de óxidos de nitrogênio (NO + NO2) durante a combustão de carvão mineral com adição de calcário dolomítico como adsorvente em leito fluidizado circulante (LFC). As variáveis de influência estudadas foram o excesso de ar, que variou entre 18 e 32 %, e a relação molar cálcio enxofre (Ca/S) que variou entre 0 e 2. A quantificação das emissões de NOx foi realizada em condições de regime estacionário através da técnica de detecção por infravermelho não dispersivo (NDIR). Perfis de temperatura e pressão foram medidos durante a realização dos experimentos. A combustão foi mantida a uma temperatura média do riser de 840 ºC e velocidade superficial do gás próxima de 9 m.s-1. Utilizou-se um Delineamento Composto Central Rotacional (DCCR) para o planejamento dos experimentos mediante determinação das variáveis de influência e seus limites de operação. Um total de treze experimentos foram realizados, sendo onze deles relativos ao planejamento experimental. A influência do parâmetro relação molar Ca/S foi mais significativa quando comparada à influência do excesso de ar. O aumento da razão Ca/S provocou acréscimo nas emissões de NOx, enquanto a redução do excesso de ar provocou a diminuição das emissões. Os resultados obtidos nesta pesquisa apontam para uma região de otimização, buscando-se a minimização das emissões de NOx que pode ser alcançada pela utilização de valores baixos de excesso de ar (18 %) e relação Ca/S de 0,6, uma vez que para relações maiores, a emissão de SO2 foi praticamente nula, destacando o elevado poder de remoção do enxofre por este calcário. / Abstract: This work reports an experimental study concerning NOx emissions from brazilian coal combustion with limestone addition in circulating fluidized bed as a function of operational parameters excess air (18 to 32 %) and Ca/S molar ratio (0 to 2). The NOx concentration was achieved at steady state operation through a non-dispersive infrared (NDIR) detection technique. Profiles of temperature and pressure were measured. Bed temperature around 840 ºC and superficial gas velocity around 9 m.s-1 were conditions maintained at the experiments. Central Composite Rotational Design has been used for planning the experiments according to the knowledge of influence variables on combustion process and its operational limits. A total of thirteen experiments were carried out. The influence of Ca/S molar ratio on NOx emissions was greater than air excess influence. Increasing Ca/S molar ratio it was observed tha NOx emissions also rise, meanwhile decreasing air excess factor leds a reduction on NOx emissions. Results pointed to a optimizing area, seeking to minimize NOx concentrations that can be achieved with low air excess (18 %) and Ca/S molar ratio of 0.6, since for larger ratios, the SOx emissions was insignificant, highlighting the limestone's high efficiency to sulfur capture. / Mestrado / Termica e Fluidos / Mestre em Engenharia Mecânica

M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Strict environmental regulation on flue gas emission has led to the implementation of FGD technologies in power stations. Wet FGD technology is commonly used because it has high SO2 removal efficiency, high sorbent utilization and due to availability of the sorbent (limestone) used. SO2 is removed by passing flue gas through the absorber where it reacts with the slurry containing calcium ions which is obtained by dissolution. This study presents the findings of the dissolution of a calcium-based material (limestone) for wet FGD process. This was done using a pH stat apparatus and adipic acid as acid titrant. Adipic acid was used because of its buffering effect in wet FGD process. The conditions used for this study are similar to what is encountered in a wet FGD process. The extent of dissolution was determined by analyzing the amount of calcium ions in solution at different dissolution periods. The dissolution kinetics were correlated to the shrinking core model and it was found out that chemical reaction at the surface of the particle is the rate controlling step. This study also investigated the dissolution of coal fly ash and bottom ash. Their dissolution kinetics showed that the diffusion through the product layer was the rate controlling step due to an ash layer formed around the particle. The formation of ash layer was attributed to pozzolanic reaction products which is calcium-alumino-silicate (anorthite) compounds were formed after dissolution. The effect of fly ash on the dissolution of rate of limestone was also studied using response surface methodology. Limestone reactivity was found to increase with increase in the amount of fly ash added and the pH was found to be strong function of the rate constant compared to other dissolution variables. The presence of silica and alumina in fly ash led to a significant increase in the specific surface area due to hydration products formed after dissolution. / Eskom

This master’s thesis is concerned with design of a heat exchanger for a unit with gas turbine. The pressurized air from the compressor is heated with flue gases from gasification and subsequent combustion of wooden biomass. Then it is led to the expansion turbine. For thermal and hydraulic calculations a program named HTRI Xchanger Suite® has been used. The thesis includes a brief description of heat exchangers, description of the used program, calculation and selection of input data, solving and conclusions. It contains also a layout of the exchanger.

Abstract in English / Incineration is still a widely utilised method for treating healthcare risk waste in the Republic of South Africa. As much as incinerators are needed, the fact that they are still a critical source of hazardous toxic air pollutants that are not easy to manage cannot be disregarded. The Ministry of Environmental Affairs has promulgated a new regulation for General and Hazardous Waste Thermal Treatment. This exceedingly stringent air pollution legislation requires that existing incinerators be modified or redesigned to meet the new air quality standards, or face closure in the event that they fail to comply. The regulation contains strict emission requirements for concentrations of stack gases such as CO2, NO2, NOx, HCl, HF, CO, SO2, as well as TOC and PM. To be certain that emissions are within the standard, incineration facilities are instructed to reduce the acid gas emissions and to have permanent on-line monitoring equipment for stack testing of regulated pollutants. Since the promulgation of the new legislation in April 2015, none of the incinerators in South Africa has been able to achieve the new requirements. This study, based on the quantitative approach, was conducted in search of a cost-effective method of controlling acid gas emissions from incinerators without major adjustments to the plants. During the study, 60 kg of sorbacal Ca(OH)2 was injected into a lime feeder every day. A variable speed drive was used to inject Ca(OH)2 into the furnace continuously at a rate of between 2.5 kg/h and 3.5 kg/h. The temperature was maintained between 850°C and 1200°C with the use of four gas burners. Two manual blowers were utilised to ensure a continuous flow of Ca(OH)2 into the reaction chamber and filtration system. Comparative analysis was done to compare gas emission levels before and after the use of hydrated lime. Descriptive statistics were used to compute the mean, frequency and percentages, while Wilcoxon sign rank test established whether hydrated lime was significant in reducing gaseous emissions or not. Wilcoxon sign rank test showed a statistically significant difference (P<0.05) in the reduction of all gaseous emissions using hydrated lime, except particulate matter where there was a significant increase in emissions. This technology was able to achieve high removal efficiency of 97% for HCl, 86% for HF, 83% for NOx, 87% for SO2 and 74% for NO2. The optimum temperature for SO2 and NOx was 1020°C. For HCl it was between 1190°C and 1200°C, and for NO2 it was between 1120°C and 1200°C. The amount of particulate matter increased along with the concentration of the Ca(OH)2 injections. Ca(OH)2 was found to be cost effective in the controlling and capturing of gaseous emissions. It is recommended that combustion requirements, such as heat, oxygen and turbulence, be considered to reduce the amount of gases generated during the incineration of healthcare risk waste. It is also recommended that electrostatic precipitators be used instead of fabric filters to improve the efficiency of capturing the particulate matter. / Environmental Sciences / M.Sc. (Environmental Science)