Simulação de um processo de pirólise rápida de biomassa

Mestrado em Engenharia Química - Ramo Optimização Energética na Indústria Química

Calcination of aluminum hydroxide over pressure and residence time

This work investigates the possible effect of pressure and residence time to the reaction of aluminum hydroxide into aluminum oxide. Various pressurized conditions are used as well as the help of various residence times. The aim is to increase the conversion of the reaction with the use of different pressures and residence times. The tests were performed with a laboratory scale fluidized bed reactor at the Outotec R&D Center in Frankfurt. Additional test work such as particle size analysis and differential thermal analysis were also carried out. Some calcined samples were also characterized with X-ray diffraction at the University of Auckland to obtain a reaction pathway when using pressurized conditions. All of the results are then compared with previous results.

Diagnostiikkamenetelmät höyrykattilan leijukerroksen tilan ja käytettävyysongelmien tunnistamiseksi

Diplomityön tavoitteena oli tutkia höyrykattiloiden leijukerrosten käytettävyysongelmia ja kirjallisuudesta löytyvien diagnostiikkamenetelmien toimivuutta leijukerroksen tilan ja käytettävyysongelmien tunnistamiseksi. Diagnostiikkamenetelmien toimivuutta testattiin VTT:n kiertoleijukoelaitteen prosessimittauksiin perustuen. Analysoinnissa käytettiin prosessimittauksia, jotka ovat yleisesti käytössä energiantuotannon leijukerroskattiloissa. Analysoitavina koeajotapauksina olivat kylmäkokeet partikkelikokojakaumaltaan vaihtelevalle leijutusmateriaalille, tuhkapartikkelien aiheuttama petimateriaalin karkeneminen ja agglomeroituminen, sekä vaihtelevien ajoarvojen vaikutus leijukerroksen hydrodynaamiseen käyttäytymiseen. Kokeellisesta osiosta saaduista tuloksista selvisi leijutusilman tilavuusvirran, petimassan ja partikkelikoon vaikutus analysoitavaan prosessimittaukseen. Tuloksista oli havaittavissa myös kiertävän petimateriaalin ja pohjapedin osuuksien vaikutus mitattuun painesignaaliin. Petipartikkelien agglomeroitumisen ja karkenemisen todettiin lisäävän kiertoleijukoelaitteistossa nousuputken pohjapedin määrää suhteessa kiertävään petimateriaaliin, mikä voitiin havaita painemittauksista.

Caracterização de cinza obtida por combustão de casca de arroz em reator de leito fluidizado

The rice husk combustion in a bubbling and atmospheric fluidized bed reactor was investigated. This paper presents the rice husk ash characterization employing the techniques of X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM) among others. After combustion, a rice husk ash containing 93% amorphous silica and <3% unburned char was produced. Methods usually applied to fixed bed considering external sources of energy and high reaction times were employed. Thus, the potential of this type of reactors with respect to speed, continuity and self-sufficiency energy of the process was shown.

Corrosion behaviour of boiler tube materials during combustion of fuels containing Zn and Pb

Många förbränningsanläggningar som bränner utmanande bränslen såsom restfraktioner och avfall råkar ut för problem med ökad korrosion på överhettare och/eller vattenväggar pga. komponenter i bränslena som är korrosiva. För att minimera problemen i avfallseldade pannor hålls ångparametrarna på en relativt låg nivå, vilket drastiskt minskar energiproduktionen. Beläggningarna i avfallseldade pannor består till största delen av element som är förknippade med högtemperaturkorrosion: Cl, S, alkalimetaller, främst K och Na, och tungmetaller som Pb och Zn, och det finns också indikationer av Br-förekomst. Det låga ångtrycket i avfallseldade pannor påverkar också stålrörens temperatur i pannväggarna i eldstaden. I dagens läge hålls temperaturen normalt vid 300-400 °C. Alkalikloridorsakad (KCl, NaCl) högtemperaturkorrosion har inte rapporterats vara relevant vid såpass låga temperaturer, men närvaro av Zn- och Pb-komponenter i beläggningarna har påvisats förorsaka ökad korrosion redan vid 300-400 °C. Vid förbränning kan Zn och Pb reagera med S och Cl och bilda klorider och sulfater i rökgaserna. Dessa tungmetallföreningar är speciellt problematiska pga. de bildar lågsmältande saltblandningar. Dessa lågsmältande gasformiga eller fasta föreningar följer rökgasen och kan sedan fastna eller kondensera på kallare ytor på pannväggar eller överhettare för att sedan bilda aggressiva beläggningar. Tungmetallrika (Pb, Zn) klorider och sulfater ökar risken för korrosion, och effekten förstärks ytterligare vid närvaro av smälta. Motivet med den här studien var att få en bättre insikt i högtemperaturkorrosion förorsakad av Zn och Pb, samt att undersöka och prediktera beteendet och motståndskraften hos några stålkvaliteter som används i överhettare och pannväggar i tungmetallrika förhållanden och höga materialtemperaturer. Omfattande laboratorie-, småskale- och fullskaletest utfördes. Resultaten kan direkt utnyttjas i praktiska applikationer, t.ex. vid materialval, eller vid utveckling av korrosionsmotverkande verktyg för att hitta initierande faktorer och förstå deras effekt på högtemperaturkorrosion.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Monitoramento de 24 horas do desempenho de reator aeróbio de leito fluidizado trifásico na remoção de amônio num sistema de recirculação para produção de tilápia

O objetivo deste trabalho foi monitorar o desempenho de remoção de nitrogênio amoniacal no tratamento das águas residuárias da produção intensiva de tilápia nilótica em sistema com recirculação de água. O sistema foi constituído por um sedimentador convencional e um reator aeróbio de leito fluidizado trifásico com circulação, operados com tempos de detenção hidráulica de 176.4 e 11.9 minutos respectivamente. O meio suporte utilizado no reator foi o carvão ativado granular com densidade aparente de 1.64 g/cm3 e tamanho efetivo de 0.34 mm; a concentração do meio suporte no reator foi mantida constante em 80 g/L. A eficiência média de remoção do nitrogênio amoniacal total foi de 41.2%. O sistema avaliado é uma alternativa efetiva para o reuso da água em sistemas de recirculação para aqüicultura. Embora a variabilidade das concentrações do nitrogênio amoniacal afluente cujo valor médio foi de 0.136 mg/L, o efluente do reator conservou as características de qualidade da água estáveis, com concentrações médias de nitrogênio amoniacal de 0.079 mg/L e do oxigênio dissolvido de 6.70 mg/L, recomendáveis para a criação dos peixes e nas faixas de valores permitidos pela legislação Brasileira (Resolução CONAMA No. 357 de março 5 de 2005) para lançamento de efluentes finais nos corpos de água receptores.

Desempeño de tanques decantadores de sólidos en un sistema de recirculación para producción de tilapia

To compare the removal efficiency of solids, turbidity and apparent color between a conventional and a column settling tanks in a recirculating aquaculture system (RAS) for tilapia farming. Materials and methods. Tilapia with a stocking density between 30 and 33 kg/m3 were cultured in a RAS consisting of a water level control box, PVC piping system, three plastic tanks for culture, conventional horizontal flow settling tank (Con.ST), column vertical flow settling tank (Col.ST), three phase fluidized bed reactor, oxygen transfer reactor, air compressor, air blower, centrifugal pump. The Con.ST operated at a volume of 1.4 m3 and hydraulic retention time (HRT) of 2.94 h; and was drained weekly for washing and sludge collection, representing a 55%discharge of system water volume. The Col.ST operated with a volume of 0.30 m3 and HRT of 0.553 h. Three daily partial draining operations were executed, representing a discharge of 50% of the system volume. Results. The mean solids removal efficiencies were: 34.01 and 44.44%for total solids; 64.45 and 71.71% for suspended solids; 21.10 and 45.65% volatile solids; 65.51% and 62.79% for turbidity; and 56.37 and 50.91% for apparent color, respectively for Con.ST and Col.ST. Conclusions. The two settling devices are useful on removal of the studied parameters and presented similar performance on turbidity and apparent color removal; however, the Col.ST was more efficient than Con.ST for solids removal, requires less space, less volume and requires less discharge water volume, displaying feasibility for its use on RAS.

Efeito da concentração do meio suporte e relação entre áreas no desempenho de reatores aeróbios de leito fluidizado com circulação interna no tratamento de esgoto doméstico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Utilização de reator aeróbio de leito fluidizado com circulação em tubos concêntricos no tratamento de águas residuarias da produção intensiva de tilapia com recirculação da água tratada

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise e demonstração do comportamento do escoamento bifásico gás-sólido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Uso de invertase imobilizada em pó de sabugo de milho para produção de açúcar invertido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da fluidodinâmica de uma mistura de sólidos em um leito fluidizado gás-sólido

Fluidization consists in a bed of solid particles acquire fluid behavior by using a fluid (in this case air) flowing through the solid particles. Because of this, it can be a good mix of these materials, as well as to show increased rates of heat and mass transport. The fluid flowing through the spaces between the particles gives an interstitial velocity, that if is too low does not cause movement of the particulates. The gradual increase in speed will generate small vibrations between the particles promotes its fluidization. Our study focus in the fluid state of solid bed , when the fluid velocity reaches a state where the drag forces are sufficient to support the weight of the solid particles making these solids behave like fluids . Knowledge of the minimum velocity required to fluidize that particles is of great importance since below this speed there is no fluidization, and far above it, the solids are carried out of the bed. The fluidized bed reactor is widely used in physics and engineering, particularly in gas-solid fluidization, with emphasis on thermochemical processes

Continuous enzymatic interesterification of milkfat with soybean oil produces a highly spreadable product rich in polyunsaturated fatty acids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Understanding and improving the chemical vapor deposition process for solar grade silicon production

Esta Tesis Doctoral se centra en la investigación del proceso de producción de polisilicio para aplicaciones fotovoltaicas (FV) por la vía química; mediante procesos de depósito en fase vapor (CVD). El polisilicio para la industria FV recibe el nombre de silicio de grado solar (SoG Si). Por un lado, el proceso que domina hoy en día la producción de SoG Si está basado en la síntesis, destilación y descomposición de triclorosilano (TCS) en un reactor CVD -denominado reactor Siemens-. El material obtenido mediante este proceso es de muy alta pureza, pero a costa de un elevado consumo energético. Así, para alcanzar los dos principales objetivos de la industria FV basada en silicio, bajos costes de producción y bajo tiempo de retorno de la energía invertida en su fabricación, es esencial disminuir el consumo energético de los reactores Siemens. Por otro lado, una alternativa al proceso Siemens considera la descomposición de monosilano (MS) en un reactor de lecho fluidizado (FBR). Este proceso alternativo tiene un consumo energético mucho menor que el de un reactor Siemens, si bien la calidad del material resultante es también menor; pero ésta puede ser suficiente para la industria FV. A día de hoy los FBR deben aún abordar una serie de retos para que su menor consumo energético sea una ventaja suficiente comparada con otras desventajas de estos reactores. En resumen, la investigación desarrollada se centra en el proceso de depósito de polysilicio por CVD a partir de TCS -reactor Siemens-; pero también se investiga el proceso de producción de SoG Si en los FBR exponiendo las fortalezas y debilidades de esta alternativa. Para poder profundizar en el conocimiento del proceso CVD para la producción de polisilicio es clave el conocimiento de las reacciones químicas fundamentales y cómo éstas influencian la calidad del producto resultante, al mismo tiempo que comprender los fenómenos responsables del consumo energético. Por medio de un reactor Siemens de laboratorio en el que se llevan a cabo un elevado número de experimentos de depósito de polisilicio de forma satisfactoria se adquiere el conocimiento previamente descrito. Se pone de manifiesto la complejidad de los reactores CVD y de los problemas asociados a la pérdidas de calor de estos procesos. Se identifican las contribuciones a las pérdidas de calor de los reactores CVD, éstas pérdidas de calor son debidas principalmente a los fenómenos de radiación y, conducción y convección vía gases. En el caso de los reactores Siemens el fenómeno que contribuye en mayor medida al alto consumo energético son las pérdidas de calor por radiación, mientras que en los FBRs tanto la radiación como el calor transferido por transporte másico contribuyen de forma importante. Se desarrolla un modelo teórico integral para el cálculo de las pérdidas de calor en reactores Siemens. Este modelo está formado a su vez por un modelo para la evaluación de las pérdidas de calor por radiación y modelos para la evaluación de las pérdidas de calor por conducción y convección vía gases. Se ponen de manifiesto una serie de limitaciones del modelo de pérdidas de calor por radiación, y se desarrollan una serie de modificaciones que mejoran el modelo previo. El modelo integral se valida por medio un reactor Siemens de laboratorio, y una vez validado se presenta su extrapolación a la escala industrial. El proceso de conversión de TCS y MS a polisilicio se investiga mediante modelos de fluidodinámica computacional (CFD). Se desarrollan modelados CFD para un reactor Siemens de laboratorio y para un prototipo FBR. Los resultados obtenidos mediante simulación son comparados, en ambos casos, con resultados experimentales. Los modelos desarrollados se convierten en herramientas para la identificación de aquellos parámetros que tienen mayor influencia en los procesos CVD. En el caso del reactor Siemens, ambos modelos -el modelo integral y el modelado CFD permiten el estudio de los parámetros que afectan en mayor medida al elevado consumo energético, y mediante su análisis se sugieren modificaciones para este tipo de reactores que se traducirían en un menor número de kilovatios-hora consumidos por kilogramo de silicio producido. Para el caso del FBR, el modelado CFD permite analizar el efecto de una serie de parámetros sobre la distribución de temperaturas en el lecho fluidizado; y dicha distribución de temperaturas está directamente relacionada con los principales retos de este tipo de reactores. Por último, existen nuevos conceptos de depósito de polisilicio; éstos se aprovechan de la ventaja teórica de un mayor volumen depositado por unidad de tiempo -cuando una mayor superficie de depósito está disponible- con el objetivo de reducir la energía consumida por los reactores Siemens. Estos conceptos se exploran mediante cálculos teóricos y pruebas en el reactor Siemens de laboratorio. ABSTRACT This Doctoral Thesis comprises research on polysilicon production for photovoltaic (PV) applications through the chemical route: chemical vapor deposition (CVD) process. PV polysilicon is named solar grade silicon (SoG Si). On the one hand, the besetting CVD process for SoG Si production is based on the synthesis, distillation, and decomposition of thriclorosilane (TCS) in the so called Siemens reactor; high purity silicon is obtained at the expense of high energy consumption. Thus, lowering the energy consumption of the Siemens process is essential to achieve the two wider objectives for silicon-based PV technology: low production cost and low energy payback time. On the other hand, a valuable variation of this process considers the use of monosilane (MS) in a fluidized bed reactor (FBR); lower output material quality is obtained but it may fulfil the requirements for the PV industry. FBRs demand lower energy consumption than Siemens reactors but further research is necessary to address the actual challenges of these reactors. In short, this work is centered in polysilicon CVD process from TCS -Siemens reactor-; but it also offers insights on the strengths and weaknesses of the FBR for SoG Si production. In order to aid further development in polysilicon CVD is key the understanding of the fundamental reactions and how they influence the product quality, at the same time as to comprehend the phenomena responsible for the energy consumption. Experiments conducted in a laboratory Siemens reactor prove the satisfactory operation of the prototype reactor, and allow to acquire the knowledge that has been described. Complexity of the CVD reactors is stated and the heat loss problem associated with polysilicon CVD is addressed. All contributions to the energy consumption of Siemens reactors and FBRs are put forward; these phenomena are radiation and, conduction and convection via gases heat loss. In a Siemens reactor the major contributor to the energy consumption is radiation heat loss; in case of FBRs radiation and heat transfer due to mass transport are both important contributors. Theoretical models for radiation, conduction and convection heat loss in a Siemens reactor are developed; shaping a comprehensive theoretical model for heat loss in Siemens reactors. Limitations of the radiation heat loss model are put forward, and a novel contribution to the existing model is developed. The comprehensive model for heat loss is validated through a laboratory Siemens reactor, and results are scaled to industrial reactors. The process of conversion of TCS and MS gases to solid polysilicon is investigated by means of computational fluid-dynamics models. CFD models for a laboratory Siemens reactor and a FBR prototype are developed. Simulated results for both CVD prototypes are compared with experimental data. The developed models are used as a tool to investigate the parameters that more strongly influence both processes. For the Siemens reactors, both, the comprehensive theoretical model and the CFD model allow to identify the parameters responsible for the great power consumption, and thus, suggest some modifications that could decrease the ratio kilowatts-hour per kilogram of silicon produced. For the FBR, the CFD model allows to explore the effect of a number of parameters on the thermal distribution of the fluidized bed; that is the main actual challenge of these type of reactors. Finally, there exist new deposition surface concepts that take advantage of higher volume deposited per time unit -when higher deposition area is available- trying to reduce the high energy consumption of the Siemens reactors. These novel concepts are explored by means of theoretical calculations and tests in the laboratory Siemens prototype.