USE OF SOLAR ENERGY IN THE TREATMENT OF WATER CONTAMINATED WITH PHENOL BY PHOTOCHEMICAL PROCESSES

The solar driven photo-Fenton process for treating water containing phenol as a contaminant has been evaluated by means of pilot-scale experiments with a parabolic trough solar reactor (PTR). The effects of Fe(II) (0.04-1.0 mmol L(-1)), H(2)O(2) (7-270 mmol L(-1)), initial phenol concentration (100 and 500 mg C L(-1)), solar radiation, and operation mode (batch and fed-batch) on the process efficiency were investigated. More than 90% of the dissolved organic carbon (DOC) was removed within 3 hours of irradiation or less, a performance equivalent to that of artificially-irradiated reactors, indicating that solar light can be used either as an effective complementary or as an alternative source of photons for the photo-Fenton degradation process. A non-linear multivariable model based on a neural network was fit to the experimental results of batch-mode experiments in order to evaluate the relative importance of the process variables considered on the DOC removal over the reaction time. This included solar radiation, which is not a controlled variable. The observed behavior of the system in batch-mode was compared with fed-batch experiments carried out under similar conditions. The main contribution of the study consists of the results from experiments under different conditions and the discussion of the system behavior. Both constitute important information for the design and scale-up of solar radiation-based photodegradation processes.

Estudo da eficiência da desinfecção solar de águas residuárias domésticas em reatores de diferentes colorações

Pós-graduação em Agronomia (Irrigação e Drenagem) - FCA

Feasibility Study of a Solar Reactor for Phenol Treatment by the Photo-Fenton process in Aqueous Solution

Solar reactors can be attractive in photodegradation processes due to lower electrical energy demand. The performance of a solar reactor for two flow configurations, i.e., plug flow and mixed flow, is compared based on experimental results with a pilot-scale solar reactor. Aqueous solutions of phenol were used as a model for industrial wastewater containing organic contaminants. Batch experiments were carried out under clear sky, resulting in removal rates in the range of 96100?%. The dissolved organic carbon removal rate was simulated by an empirical model based on neural networks, which was adjusted to the experimental data, resulting in a correlation coefficient of 0.9856. This approach enabled to estimate effects of process variables which could not be evaluated from the experiments. Simulations with different reactor configurations indicated relevant aspects for the design of solar reactors.

Comparative effectiveness of solar disinfection using small-scale batch reactors with reflective, absorptive and transmissive rear surfaces

This study investigated the enhancement of solar disinfection using custom-made batch reactors with reflective (foil-backed) or absorptive (black-backed) rear surfaces, under a range of weather conditions in India. Plate counts of Escherichia coli ATCC11775 were made under aerobic conditions and under conditions where reactive oxygen species (ROS) were neutralised, i.e. in growth medium supplemented with 0.05% w/v sodium pyruvate plus incubation under anaerobic conditions. While the addition of either an absorptive or a reflective backing enhanced reactor performance under strong sunlight, the reflective reactor was the only system to show consistent enhancement under low sunlight, where the process was slowest. Counts performed under ROS-neutralised conditions were slightly higher than those in air, indicating that a fraction of the cells become sub-lethally injured during exposure to sunlight to the extent that they were unable to grow aerobically. However, the influence of this phenomenon on the dynamics of inactivation was relatively small

Deposition reactors for solar grade silicon: a comparative thermal analysis of a Siemens reactor and a fluidized bed reactor

Polysilicon production costs contribute approximately to 25-33% of the overall cost of the solar panels and a similar fraction of the total energy invested in their fabrication. Understanding the energy losses and the behaviour of process temperature is an essential requirement as one moves forward to design and build large scale polysilicon manufacturing plants. In this paper we present thermal models for two processes for poly production, viz., the Siemens process using trichlorosilane (TCS) as precursor and the fluid bed process using silane (monosilane, MS).We validate the models with some experimental measurements on prototype laboratory reactors relating the temperature profiles to product quality. A model sensitivity analysis is also performed, and the efects of some key parameters such as reactor wall emissivity, gas distributor temperature, etc., on temperature distribution and product quality are examined. The information presented in this paper is useful for further understanding of the strengths and weaknesses of both deposition technologies, and will help in optimal temperature profiling of these systems aiming at lowering production costs without compromising the solar cell quality.

Degradação do fungicida tiofanato metílico pelo processo foto-Fenton em reatores anular e solar

Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of São Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor

Determining the oscillation parameters by solar neutrinos and KamLAND

The neutrino oscillation experiment KamLAND has provided us with the first evidence for e disappearance, coming from nuclear reactors. We have combined their data with all solar neutrino data, assuming two flavor neutrino mixing, and obtained allowed parameter regions which are compatible with the so-called large mixing angle MSW solution to the solar neutrino problem. The allowed regions in the plane of mixing angle and mass squared difference are now split into two islands at 99% C.L. We have speculated how these two islands can be distinguished in the near future. We have shown that a 50% reduction of the error on SNO neutral-current measurement can be important in establishing in each of these islands the true values of these parameters lie, We also have simulated KamLAND positron energy spectrum after I year of data taking, assuming the current best fitted values of the oscillation parameters, combined it the with current solar neutrino data and showed how these two split islands can be modified. (C) 2003 Published by Elsevier B.V. B.V.

On track for solar grade silicon through a siemens process-type laboratory reactor: operating conditions and energy savings

Polysilicon cost impacts significantly on the photovoltaics (PV) cost and on the energy payback time. Nowadays, the besetting production process is the so called Siemens process, polysilicon deposition by chemical vapor deposition (CVD) from Trichlorosilane. Polysilicon purification level for PV is to a certain extent less demanding that for microelectronics. At the Instituto de Energía Solar (IES) research on this subject is performed through a Siemens process-type laboratory reactor. Through the laboratory CVD prototype at the IES laboratories, valuable information about the phenomena involved in the polysilicon deposition process and the operating conditions is obtained. Polysilicon deposition by CVD is a complex process due to the big number of parameters involved. A study on the influence of temperature and inlet gas mixture composition on the polysilicon deposition growth rate, based on experimental experience, is shown. Moreover, CVD process accounts for the largest contribution to the energy consumption of the polysilicon production. In addition, radiation phenomenon is the major responsible for low energetic efficiency of the whole process. This work presents a model of radiation heat loss, and the theoretical calculations are confirmed experimentally through a prototype reactor at our disposal, yielding a valuable know-how for energy consumption reduction at industrial Siemens reactors.

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.

Conceptual Design of a Circulating Fluidized Bed Reactor as a Thermochemical Thermal Energy Storage System for Applications in Concentrated Solar Thermal Power Plants

Thesis (Master's)--University of Washington, 2016-08

Molecular and hybrid systems for solar-to-chemical energy conversion

My Ph.D. thesis was dedicated to the exploration of different paths to convert sunlight into the shape of chemical bonds, by the formation of solar fuels. During the past three years, I have focused my research on two of these, namely molecular hydrogen H2 and the reduced nicotinamide adenine dinucleotide enzyme cofactor NAD(P)H. The first could become the ideal energy carrier for a truly clean energy system; it currently represents the best chance to liberate humanity from its dependence on fossil fuels. To address this, I studied different systems which can achieve proton reduction upon light absorption. More specifically, part of my work was aimed to the development of a cost-effective and stable catalyst in combination with a well-known photochemical cycle. To this extent, I worked on transition metal oxides which, as demonstrated in this work, have been identified as promising H2 evolution catalysts, showing excellent activity, stability, and previously unreported versatility. Another branch of my work on hydrogen production dealt with the use of a new class of polymeric semiconductor materials to absorb light and convert it into H2. The second solar fuel mentioned above is a key component of the most powerful methods for chemical synthesis: enzyme catalysis. The high cost of the reduced forms prohibits large-scale utilization, so artificial photosynthetic approaches for regenerating it are being intensively studied. The first system I developed exploits the tremendous reducing properties of a scarcely known ruthenium complex which is able to reduce NAD+. Lastly, I sought to revert the classical role of the sacrificial electron donor to an active component of the system and, to boost the process, I build up an autonomous microfluidic system able to generate highly reproducible NAD(P)H amount, demonstrating the superior performance of microfluidic reactors over batch and representing another successful photochemical NAD(P)H regeneration system.

Remediation Of 17-α-ethinylestradiol Aqueous Solution By Photocatalysis And Electrochemically-assisted Photocatalysis Using Tio2 And Tio2/wo3 Electrodes Irradiated By A Solar Simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Dosimetria esporular: Bacillus subtilis TKJ6312 como biossensor de radiação solar biologicamente ativa

Since 2000, spore dosimetry and spectral photometry have been performed in parallel at the Southern Space Observatory, São Martinho da Serra (Southern Brazil). A comparative study involving data from Punta Arenas - Chile (53.2º S), São Martinho da Serra (29.5º S), Padang - Indonesia (0.9ºS), Brussels - Belgium (50.9º N) and Kiyotake - Japan (31.9º N) from 2000 to 2006 is presented. The Spore Inactivation Doses presented the higher values in summer (973 ± 73 for Punta Arenas and 4,369 ± 202 for São Martinho da Serra, as well 1,402 ± 170 and 3,400 ± 1,674 for Brussels and Kiyotake, respectively). The simplicity, robustness and high resistance of bacterial spores makes the biosensor an potential biological tool for UV-B monitoring.

Turbulent magnetic pumping in a Babcock-Leighton solar dynamo model

Context. The turbulent pumping effect corresponds to the transport of magnetic flux due to the presence of density and turbulence gradients in convectively unstable layers. In the induction equation it appears as an advective term and for this reason it is expected to be important in the solar and stellar dynamo processes. Aims. We explore the effects of turbulent pumping in a flux-dominated Babcock-Leighton solar dynamo model with a solar-like rotation law. Methods. As a first step, only vertical pumping has been considered through the inclusion of a radial diamagnetic term in the induction equation. In the second step, a latitudinal pumping term was included and then, a near-surface shear was included. Results. The results reveal the importance of the pumping mechanism in solving current limitations in mean field dynamo modeling, such as the storage of the magnetic flux and the latitudinal distribution of the sunspots. If a meridional flow is assumed to be present only in the upper part of the convective zone, it is the full turbulent pumping that regulates both the period of the solar cycle and the latitudinal distribution of the sunspot activity. In models that consider shear near the surface, a second shell of toroidal field is generated above r = 0.95 R(circle dot) at all latitudes. If the full pumping is also included, the polar toroidal fields are efficiently advected inwards, and the toroidal magnetic activity survives only at the observed latitudes near the equator. With regard to the parity of the magnetic field, only models that combine turbulent pumping with near-surface shear always converge to the dipolar parity. Conclusions. This result suggests that, under the Babcock-Leighton approach, the equartorward motion of the observed magnetic activity is governed by the latitudinal pumping of the toroidal magnetic field rather than by a large scale coherent meridional flow. Our results support the idea that the parity problem is related to the quadrupolar imprint of the meridional flow on the poloidal component of the magnetic field and the turbulent pumping positively contributes to wash out this imprint.