Capacidad y comportamiento de la adsorción de fenol en caolines naturales y modificados

En la actualidad las industrias químicas, farmacéuticas y clínicas, originan contaminantes en aguas superficiales, aguas subterráneas y suelos de nuestro país, como es el caso del fenol, contaminante orgánico común y altamente dañino para los organismos, incluso a bajas concentraciones. Existen en el mercado diferentes metodologías para minimizar la contaminación pero muchos de estos procesos tienen un alto coste, generación de contaminantes, etc. La adsorción de contaminantes por medio de arcillas es un método ampliamente utilizado, encontrándose eficaz y económico. Pero la dificultad de adsorber un contaminante orgánico como el fenol motiva la creación de un material llamado organoarcillas. Las organoarcillas son arcillas modificadas con un surfactante, a su vez, los surfactantes son moléculas orgánicas que confieren a la superficie de la arcilla carga catiónica en lugar de aniónica, haciendo más fácil la adsorción de fenol. Para esta tesis se ha elegido el caolín como material adsorbente, fácilmente disponible y relativamente de bajo coste. Se ha trabajado con: arenas de caolín, material directo de la extracción, y caolín lavado, originado del proceso de lavado de las arenas de caolín. Ambos grupos se diferencian fundamentalmente por su contenido en cuarzo, ampliamente mayor en las arenas de caolín. Con el objetivo de desarrollar un material a partir del caolín y arenas de éste con capacidad de retención de contaminates, en concreto, fenol, se procedió a modificar los materiales de partida mediante tratamientos térmicos, mecánicos y/o químicos, dando lugar a compuestos con mayor superficie química reactiva. Para ello se sometió el caolín y las arenas caoliníferas a temperaturas de 750ºC durante 3h, a moliendas hasta alcanzar su amorfización, y/o a activaciones con HCl 6M o con NaOH 5M durante 3h a 90ºC. En total se obtuvieron 18 muestras, en las que se estudiaron las características físico-químicas, mineralógicas y morfológicas de cada una de ellas con el fin de caracterizarlas después de haber sufrido los tratamientos y/o activaciones químicas. Los cambios producidos fueron estudiados mediante pH, capacidad de intercambio catiónico (CEC), capacidad de adsorción de agua (WCU y CWC), distribución de tamaño de partícula (PSD), área de superficie específica (SBET), difracción de rayos X (XRD), espectroscopía infrarroja por transformada de Fourier (FTIR), métodos térmicos (TG, DTG y DTA), y microscopía electrónica de transmisión y barrido (SEM y TEM). Además se analizó los cambios producidos por los tratamientos en función de las pérdidas de Al y Si que acontece en las 18 muestras. Los resultados para los materiales derivados de la arenas caoliníferas fueron similares a los obtenidos para los caolines lavados, la diferencia radica en la cantidad de contenido de caolinita en los diferente grupos de muestras. Apoyándonos en las técnicas de caracterización se puede observar que los tratamientos térmico y molienda produce materiales amorfos, este cambio en la estructura inicial sumado a las activaciones ácida y alcalina dan lugar a pérdidas de Si y Al, ocasionando que sus propiedades físico-químicas, mineralógicas y morfológicas se vean alteradas. Un fuerte aumento es observado en las áreas superficiales y en la CEC en determinadas muestras, además entre los cambios producidos se encuentra la producción de diferentes zeolitas en porcentajes distintos con el tratamiento alcalino. Para la obtención de las organoarcillas, las 18 muestras se sometieron a la surfactación con hexadeciltrimetil amonio (HDTMA) 20 mM durante 24h a 60ºC, esta concentración de tensioactivo fue más alta que la CEC de cada muestra. Los camext bios anteriormente producidos por los tratamientos y activaciones, afectan de forma diferente en la adsorción de HDTMA, variando por tanto la adsorción del surfactante en la superficie de las muestras. Se determinó el tensioactivo en superficie por FTIR, además se realizó un análisis de componentes principales (PCA) para examinar la dependencia entre las relaciones Si/Al de las muestras en la capacidad de adsorción de tensioactivo, y para el estudio de la adsorción de HDTMA en las muestras se realizaron además del análisis termogravimétrico, aproximaciones con los modelos de Freundllich y Langmuir. Se persigue conocer las diferentes formas y maneras que tiene el tensioactivo de fijarse en la superficie de las muestras. En las organoarcillas resultantes se cuantificó el fenol adsorbido cuando éstas fueron puestas en contacto con diferentes concentraciones de fenol: 50, 500, 1000, 2000, y 2500 mg/l durante 24h. El contaminante sorbido se calculó por medio de cromatografía de gases, y se realizaron aproximaciones con los modelos de Freundllich y Langmuir. El comportamiento de adsorción de fenol en arcillas orgánicas es regido por las características de las muestras. De forma general se puede decir que las muestras de caolines lavados tienen más capacidad de adsorción de fenol que las muestras de arenas de caolín y que la activación alcalina ha proporcionado una mejora en la adsorción de fenol en los dos grupos. En consecuencia se han obtenido materiales adsorbentes heterogéneos y por tanto, con propiedades diferentes. Se ha evaluado el comportamiento global de las arenas de caolín por un lado y del caolín lavado por otro. Las arenas de caolín presentan altos niveles de cuarzo y su uso para ciertos tipos de industrias no son recomendados en ocasiones por el alto costo que el proceso de limpieza y purificación implicaría. Por ello es importante reseñar en este proyecto las aplicaciones que ofrecen algunas muestras de este grupo. Los ensayos acontecidos en esta tesis han dado lugar a las siguientes publicaciones: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno. Aceptada en Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Envío a revista sujeto a la publicación del artículo anterior. ABSTRACT Today’s chemical, pharmaceutical and clinical industries generate pollutants that affect the soils and surface and ground waters of our country. Among these, phenol is a common organic pollutant that is extremely harmful to living organisms, even at low concentrations. Several protocols exist to minimize the effects of pollutants, but most are costly procedures or even generate other pollutants. The adsorption of hazardous materials onto clays is perhaps the most used, efficient and cost-saving method available. However, organic compounds such as phenol are difficult to adsorb and this has led to the development of materials known as organoclays, which are much better at remediating organic compounds. Organoclays are clays that have been modified using a surfactant. In turn, surfactants are organic molecules that confer a cationic rather than anionic charge to the clay surface, improving it’s capacity to adsorb phenol. For this doctorate project, kaolin was selected as an adsorbent material for the removal of phenol given its easy sourcing and relatively low cost. The materials investigated were kaolin sand, a directly extracted material, and washed kaolin, which is the byproduct of the kaolin sand washing process. The main difference between the materials is their quartz content, which is much higher in the kaolin sands. To generate a product from kaolin or kaolin sand capable of retaining organic pollutants such as phenol, both materials were subjected to several heat, chemical and/or mechanical treatments to give rise to compounds with a greater reactive surface area. To this end the two starting materials underwent heating at 750ºC for 3 h, grinding to the point of amorphization and/or activation with HCl 6M or NaOH 5M for 3 h at 90ºC. These treatments gave rise to 18 processed samples, which were characterized in terms of their morphological, mineralogical, and physical-chemical properties. The behaviour of these new materials was examined in terms of their pH, cation exchange capacity (CEC), water adsorption capacity (WCU and WCC), particle size distribution (PSD), specific surface area (SBET), and their X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal (DTG, DTA) and scanning and transmission electron microscopy (SEM and TEM) properties. The changes conferred by the different treatments were also examined in terms of Al and Si losses. Results for the materials derived from kaolin sands and washed kaolin were similar, with differences attributable to the kaolinite contents of the samples. The treatments heat and grinding produced amorphous materials, which when subjected to acid or alkali activation gave rise to Si and Al losses. This in turn led to a change in physico- chemical, mineralogical and morphological properties. Some samples showed a highly increased surface area and CEC. Further, among the changes produced, alkali treatment led to the generation of zeolites in different proportions depending on the sample. To produce the organoclays, the 18 samples were surfacted with hexadecyltrimethylammonium (HDTMA) 20 mM for 24 h at 60ºC. This surfactant concentration is higher than the CEC of each sample. The amount of HDTMA adsorbed onto the surface of each sample determined by FTIR varied according to treatment. A principle components analysis (PCA) was performed to examine correlations between sample Si/Al ratios and surfactant adsorption capacity. In addition, to explore HDTMA adsorption by the samples, DTG and DTA data were fitted to Freundllich and Langmuir models. The mechanisms of surfactant attachment to the sample surface were also addressed. The amount of phenol adsorbed by the resultant organoclays was determined when exposed to different phenol concentrations: 50, 500, 1000, 2000, and 2500 mg/l for 24 h. The quantity of adsorbed pollutant was estimated by gas chromatography and the data fitted to the models of Freundllich and Langmuir. Results indicate that the phenol adsorption capacity of the surfacted samples is dependent on the sample’s characteristics. In general, the washed kaolin samples showed a greater phenol adsorption capacity than the kaolon sands and alkali activation improved this capacity in the two types of sample. In conclusion, the treatments used gave rise to adsorbent materials with varying properties. Kaolin sands showed high quartz levels and their use in some industries is not recommended due to the costs involved in their washing and purification. The applications suggested by the data obtained for some of the kaolin sand samples indicate the added value of this industrial by-product. The results of this research project have led to the following publications: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G. San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno Accepted in Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Shipment postponed, subject to the publication of the previous article.

Estudio de los materiales que componen el sistema constructivo de las viviendas del casco histórico de Maracaibo (Venezuela)

En este trabajo de investigación que se presenta para optar al grado de Doctor, se analizan y estudian los materiales que conforman las viviendas de mampostería de arenisca “Piedra de Ojo” del casco histórico de Maracaibo, Venezuela, construidas en el siglo XIX. No existe una bibliografía descriptiva técnico-constructiva del sistema constructivo, por lo que esta tesis complementa la escasa descripción estilística existente donde apenas se mencionan algunos materiales de construcción. Definido el marco histórico y las manzanas del área en donde se encontraban las viviendas preseleccionadas a estudiar, en la visita de campo se seleccionaron 12 que se encontraban en estado de deterioro, y que permitieron recolectar las muestras más fácilmente. Para realizar la caracterización y comportamientos de los diferentes materiales utilizados: piedra y morteros en los cerramientos, maderas en armaduras de tejados, techos y carpintería de puertas y ventanas, cerámicos en muros y acabados, etc. Para complementar lo antes dicho se ha dividido esta tesis en seis capítulos: En el capítulo I se desarrolla el estado del arte a nivel nacional e internacional de trabajos de investigación, similares. Se aborda la memoria histórica, que es una reseña de la evolución de la vivienda en la ciudad de Maracaibo. En el capítulo II se describe la metodología empleada en la tesis, de acuerdo a los objetivos, tanto generales como específicos de la investigación. Que ha cubierto diferentes frentes: consulta bibliográfica, levantamiento planimétrico, toma de muestras, análisis de visu, caracterización físico-química y correlación de resultados. Se ha desarrollado el trabajo tanto in situ como en laboratorio y despacho. El capítulo III presenta la caracterización de la arenisca “Piedra de Ojo”, se desarrolla: la descripción geológica y caracterización petrológica. Se reseñan los ensayos realizados en laboratorio como: caracterización de visu, caracterización petrográfica, estudio petrográfico por microcopia óptica de trasmisión, estudio petrográfico por microcopia electrónica de barrido, microscopia electrónica de barrido en modo electrones secundarios (SSE) y microscopia electrónica de barrido en modo electrones retrodispersados. También las propiedades escalares de los mampuestos y los siguientes valores: densidades, porosidades y resistencia mecánicas, entre otros. En el capítulo IV se analizan las características de los morteros aplicados en las viviendas, y la patología o lesiones que presentan. Se clasifican en tres tipos: mortero de junta o asiento, de enfoscado y revoco. Se documenta la realización de los ensayos físicos y químicos, resistencia mecánica y de granulometría; se explican sus componentes principales: conglomerante de cal, áridos y aditivos y la tecnología de fabricación, así como las características físicas, hídricas, químicas y granulométricas. El capítulo V, contiene las aplicaciones constructivas de los materiales de albañilería, Se describen otros elementos de la vivienda como; cimentaciones, muros mixtos, molduras, apliques y pinturas y finalmente pavimentos. Y en el capítulo VI se analizan las especies de madera más representativas usadas en las armaduras de las cubiertas, así como los elementos de cubrición. De igual forma se describe la carpintería de puertas y ventanas, así como sus dinteles o cargaderos de madera y se realiza la identificación anatómica, las propiedades físicas y mecánicas de las utilizadas. Entre los resultados y conclusiones se determinó que el 90% de los materiales utilizados en su construcción proceden de zonas cercanas a la construcción de la vivienda, como la formación El Milagro convertida en cantera de piedra y que el resto de los materiales provenían de la Isla de Toas y de la exportación de las islas del Caribe y de Europa como el cemento. El principal aporte de esta investigación es el análisis técnico constructivo y la caracterización física, mecánica y química de los materiales de la vivienda, con el fin de que dicha información sea usada para definir los materiales nuevos a utilizar en las restauraciones de las viviendas y en futuras líneas de investigación. ABSTRACT In this research paper submitted to opt to the degree of Doctor, the materials that make the “Piedra de Ojo” sandstone masonry houses of the historical center of Maracaibo, Venezuela, built in the XIX century, are analyzed and studied. There exists no technical-constructive descriptive literature of the constructive system, so this thesis complements the very limited existing stylistic description, where barely some construction materials are mentioned. With the historical context and the blocks of the area where the preselected houses to be studied being defined, 12 of these houses that were in a state of decay (deterioration) were selected and this condition allowed to collect samples more easily, in order to carry out the characterization and behavior of the different materials used: stone and mortars in the walls, wood trusses in roofs, ceilings and woodwork of doors and windows, walls and ceramic finishes, etc. To complement the foregoing, this thesis has been divided in six chapters: In Chapter I, the state of art at national and international levels of similar research is developed, which is a review of the evolution of housing in the city of Maracaibo. In Chapter II, the methodology used in the thesis is described, according to the research’s objectives, general and specific ones, which have covered several fronts: literature survey, planimetric survey, sampling, visu analysis, physical-chemical characterization and correlation of results. Chapter III presents the characterization of the “Piedra de Ojo” sandstone; geological description and petrologic characterization are developed. Essays performed in the laboratory are reviewed, such as: visu characterization, petrographic characaterization, petrographic study by optical microscopy of transmission, petrographic study by electronic scanning microscopy in secondary electron mode (SSE) and electron microscopy scaning by backscattered electron mode. Also scalar properties of the masonry and the following: density, porosity and mechanical resistance, among others. In Chapter IV, characteristics of the mortars used in the houses are analyzed and pathology or damages are presented. They are classified into three types: grout, cement render and plaster. Physical and chemical testing, mechanical strength and grain size (granulometric) is documented; its main components are explained: lime binder, aggregates and additives and manufacturing technology as well as the physical, water, chemical and granulometric characteristics. Chapter V contains the constructive applications of masonry materials. Other housing elements are described, such as; foundations, mixed walls, moldings, wall paintings and finally floorings (pavements). And in chapter VI the most representative species of wood used in the overhead fixtures and cover elements are analyzed. Likewise, woodwork of doors and windows and their wooden lintels or landings are described; anatomical identification and physical and mechanical properties of the ones used is made. The results and conclusions determined that 90% of the materials used in its construction came from areas near the construction of housing, such as El Milagro formation, converted into stone quarry and other materials came from the Toas Island and from the export of the Caribbean islands and Europe, such as cement. The main contribution of this research is the constructive technical analysis and physical, mechanical and chemical characterization of the materials of the houses, in order that such information is used to define the new materials to be used in the housing restoration and future research lines.

Síntese, caracterização e modificação de superfícies de sílicas mesoporosas ordenadas para captura de CO2

Processos como a purificação do metano (CH4) e a produção de hidrogênio gasoso (H2) envolvem etapas de separação de CO2. Atualmente, etanolaminas como monoetanolamina (MEA), dietanolamina (DEA), metildietanolamina (MDEA) e trietanolamina (TEA) são as substâncias mais utilizadas no processo de separação/captura de CO2 em processos industriais. Entretanto, o uso destas substâncias apresenta alguns inconvenientes devido à alta volatilidade, dificuldade de se trabalhar com material líquido, também ao alto gasto energético envolvido das etapas de regeneração e à baixa estabilidade térmica e química. Com base nessa problemática, esse trabalho teve por objetivo a síntese de um tipo de sílica mesoporosa altamente ordenada (SBA-15) de modo a utilizá-la no processo de captura de CO2. O trabalho foi dividido em quatro etapas experimentais que envolveram a síntese da SBA-15, o estudo do comportamento térmico de algumas etanolaminas livres, síntese e caracterização de materiais adsorventes preparados a partir de incorporação de etanolaminas à SBA-15 e estudo da eficiência de captura de CO2 por esses materiais. Novas alternativas de síntese da SBA-15 foram estudadas neste trabalho, visando aperfeiçoar as propriedades texturais do material produzido. Tais alternativas são baseadas na remoção do surfatante, utilizado como molde na síntese da sílica mesoporosa, por meio da extração por Soxhlet, utilizando diferentes solventes. O processo contribuiu para melhorar as propriedades do material obtido, evitando o encolhimento da estrutura que pode ser ocasionado durante a etapa de calcinação. Por meio de técnicas como TG/DTG, DSC, FTIR e Análise Elementar de C, H e N foi realizada a caracterização físico-química e termoanalítica da MEA, DEA, MDEA e TEA, visando melhor conhecer as características destas substâncias. Estudos cinéticos baseados nos métodos termogravimétricos isotérmicos e não isotérmicos (Método de Ozawa) foram realizados, permitindo a determinação de parâmetros cinéticos envolvidos nas etapas de volatilização/decomposição térmica das etanolaminas. Além das técnicas acima mencionadas, MEV, MET, SAXS e Medidas de Adsorção de N2 foram utilizadas na caraterização da SBA-15 antes e após a incorporação das etanolaminas. Dentre as etanolaminas estudadas, a TEA apresentou maior estabilidade térmica, entretanto, devido ao seu maior impedimento estérico, é a etanolamina que apresenta menor afinidade com o CO2. Diferentemente das demais etanolaminas estudadas, a decomposição térmica da DEA envolve uma reação intramolecular, levando a formação de MEA e óxido de etileno. A incorporação destes materiais à SBA-15 aumentou a estabilidade térmica das etanolaminas, uma vez que parte do material permanece dentro dos poros da sílica. Os ensaios de adsorção de CO2 mostraram que a incorporação da MEA à SBA-15 catalisou o processo de decomposição térmica da mesma. A MDEA foi a etanolamina que apresentou maior poder de captura de CO2 e sua estabilidade térmica foi consideravelmente aumentada quando a mesma foi incorporada à SBA-15, aumentando também seu potencial de captura de CO2.

Micropartículas de quitosana estruturadas com aerosil®: estabilidade, adsorção, encapsulação e liberação de substâncias ativas

Biodegradable microspheres used as controlled release systems are important in pharmaceutics. Chitosan biopolymer represents an attractive biomaterial alternative because of its physicochemical and biological characteristics. Chitosan microspheres are expected to become promising carrier systems for drug and vaccine delivery, especially for non-invasive ways oral, mucosal and transdermal routes. Controlling the swelling rate and swelling capacity of the hydrogel and improving the fragile nature of microspheres under acidic conditions are the key challenges that need to be overcomed in order to enable the exploration of the full pharmaceutical potential use of these microparticles. Many studies have focused on the modification of chitosan microsphere structures with cross-linkers, various polymers blends and new organic-inorganic hybrid systems in order to obtain improved properties. In this work, microspheres made of chitosan and nanosized hydrophobic silica (Aerosil R972) were produced by a method consisting of two steps. First, a preparation of a macroscopically homogeneous chitosan-hydrophobic silica dispersion was prepared followed by spray drying. FTIR spectroscopy, X-ray powder diffraction, differential scanning calorimetry, thermal gravimetric analysis, scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (TEM) were used to characterize the microspheres. Also, the were conducted acid stability, moisture sorption capacity, release properties and biological assays. The chitosan-hydrophobic silica composite microspheres showed improved thermal degradation, lower water affinity, better acid stability and ability to retard rifampicin and propranolol hydrochloride (drug models) release under simulated physiological conditions. In vitro biocompatibility studies indicated low cytotoxicity and low capacity to activate cell production of the pro-inflammatory mediator nitric oxide. The results show here encourage further studies on the use of the new chitosan-hydrophobic silica composite microspheres as drug carrier systems via oral or nasal routes.

Otimização da síntese do AlSBA-15 para produção de biodiesel por transesteri-ficação do óleo de coco

Stimulus encouraging the production and consumption of biodiesel favors the policy of pre-serving the environment, contributing to the reduction of greenhouse gas reducing climate change. The current trend of research in this field focuses on improving these processes with the use of heterogeneous catalysts, seeing has significant advantages such as: low contamination of products, ease of separation of the catalyst from the reaction medium, possibili-ty of reuse of the catalyst, decreased corrosion problems. The objective of this research was to optimize the synthesis of AlSBA-15 for the production of biodiesel through transesterification process via ethyl route. For the optimization of hydrothermal synthesis of type AlSBA-15 catalyst has assembled a 23 factorial experimental matrix with eleven trials. The stoichiometric amounts of starting materials were varied according to different ratios Si / Al which is a factor in the experimental design, in addition to the time and temperature of aging of the synthesis gel. The material showed the best results of characterization (SBET = 591.7 (m2 / g), Vp = 0.83 (cm3 / g), Dp = 5.59 (nm), w = 6.48 (nm) was synthesized at 100 ° C for 24 hours, with a ratio Si / Al = 10.This material was applied as a heterogeneous catalyst in the reaction of ethyl transesterification as raw coconut oil in natura. Coconut oil presented suitable for obtaining biodiesel via ethyl route.The visual aspects and physical-chemical characteristics of the reaction products show that AlSBA-15 catalyst favored the reaction. According to physical-chemical analysis the order of oxidative stability of the product of the transesterification reaction was: catalytic reaction at 1500 ° C> non-catalytic reaction at 100 ° C> 100 ° C catalytic> catalytic reaction at 200 ° C Reaction. The results of oxidative stability and kinematic viscosity shows that the biodiesel produced in the catalytic sandblasting held at 150 ° C which was maintained within the ABNT NBR 7148, ABNT NBR 10441 and EN 14112.

Aplicação da destilação simulada por cromatografia gasosa e da termogravimetria para a avaliação da influência da redução do teor de enxofre sobre as propriedades físico-químicas do óleo diesel

One of the main problems related to the use of diesel as fuel is the presence of sulfur (S) which causes environmental pollution and corrosion of engines. In order to minimize the consequences of the release of this pollutant, Brazilian law established maximum sulfur content that diesel fuel may have. To meet these requirements, diesel with a maximum sulfur concentration equal to 10 mg/kg (S10) has been widely marketed in the country. However, the reduction of sulfur can lead to changes in the physicochemical properties of the fuel, which are essential for the performance of road vehicles. This work aims to identify the main changes in the physicochemical properties of diesel fuel and how they are related to reduction of sulfur content. Samples of diesel types S10, S500 and S1800 were tested according with the methods of the American Society for Testing and Materials (ASTM). The fuels were also characterized by thermogravimetric analysis (TG) and subjected to physical distillation (ASTM D86) and simulated distillation gas chromatography (ASTM D2887). The results showed that the reduction of sulfur turned the fuel lighter and fluid, allowing a greater applicability to low temperature environments and safer for transportation and storage. Through the simulated distillation data was observed that decreasing sulfur content resulted in higher initial boiling point temperatures and the decreasing of the boiling temperature of the medium and heavy fractions. Thermogravimetric analysis showed a loss event mass attributed to volatilization or distillation of light and medium hydrocarbons. Based on these data, the kinetic behavior of the samples was investigated and it was observed that the activation energies (Ea) did not show significant changes throughout conversion. Considering the average of these energies, the S1800 had the highest Ea during the conversion and the S10 the lowest values

Síntese e caracterização de catalisadores baseados em vermiculita modificada com ferro: aplicação em processos do tipo foto-fenton

Clays are materials with specific properties that make them promising for various studies. In this work we used the vermiculite clay as support for iron compounds, in order to obtain promising materials for application in the heterogeneous type photo-Fenton process. In all, the study included six solid, starting from the vermiculite (V0) was obtained calcined vermiculite (V0-C), the mixed material (V0/β-FeOOH) formed by vermiculite more akaganeite, exchanged vermiculite (v0t-C), vermiculite impregnated Wet (V0u-C) and V0u-CL that is the solid obtained by impregnating with a back washing. The solids of the study had their physical and chemical characteristics investigated by the following characterization techniques: X-Ray Diffraction (XRD), Infrared Spectroscopy (IR), Energy Dispersive Spectroscopy (EDS), X-Ray Fluorescence Spectroscopy (XRF), UV-Vis by Diffuse Reflectance (DR UV-Vis), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The V0 material showed three distinct phases, which are the very vermiculite, hidrobiotite and biotite, the last two phases are part of the geological of formation process vermiculite. The solids obtained after the modification showed an increase in the amount of iron present in the clay, these being quantities important for application in photocatalysis. The micrographs and EDS data, show that after treatment of addition of the metal , the iron was intercalary in structure of vermiculite for solid V0t-C and V0u-C, however, this did not occur with mixed material. In the photoFenton process, was observed a maximum removal of 88.8% of the dye methylene blue coloring for the catalyst V0/β-FeOOH, while for the other solids was obtained values between 76.8 and 62.6%, compared to 37.8% of discoloration without the presence of catalyst. Therefore, it is concluded that the vermiculite clay presents as a good catalyst and iron support for the, beyond of presenting a low cost because of its high abundance.

Caracterização do material particulado e avaliação do risco ocupacional e mecanismos moleculares associados à queima artesanal da castanha de caju

Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ≥ 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-α) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.

Caracterização do material particulado e avaliação do risco ocupacional e mecanismos moleculares associados à queima artesanal da castanha de caju

Brazil is among the largest cashew nut producers of the world. However, the roasting process is still carried out artisanally, especially in the Brazilian semiarid region. In face of this occupational problem, the aim of this study was to perform a physical-chemical characterization of the particulate matter (PM) emitted by the roasting of cashew nuts, as well as to determine the occupational risk and molecular mechanisms associated. The most evident PM characteristics were the prevalence of fine particles, typical biomass burning morphologies such as tar ball and the presence of the elements K, Cl, S, Ca and Fe. In addition, atmospheric modeling analyses suggest that these particles can reach neighboring regions of the emission source. Polycyclic aromatic hydrocarbons (PAHs) with carcinogenic potential, such as benzo[a]pyrene, dibenz[a,h]anthracene, benzo[a]anthracene, benzo[b]fluoranthene, chrysene, benzo[k]fluoranthene, indeno[1,2,3-c,d]pyrene and benzo[j]fluoranthene were the most abundant PAHs found in the two air monitoring campaigns. Among the identified oxy-PAH the benzanthrone (7H-benz[d,e]anthracen-7-one) had the highest concentration and the evaluation of lifetime cancer risk showed an increase of 12 to 37 cases of cancer for every 10,000 exposed people. Chemical analysis of roasted cashew nuts identified the PAHs: phenanthrene, benzo[g,h,i]perylene, pyrene and benzo[a]pyrene, besides the 3-pentadecilfenol allergen (urushiol analogue) as prevalent. Occupational exposure to PAHs was confirmed by the increase of urinary 1-hydroxypyrene levels and genotoxic effects were evidenced by the increase on micronuclei and nuclear bud frequency in exfoliated buccal mucosa cells among the exposed workers. Other biomarkers of effects such as karyorrhexis, pyknotic, karyolytic, condensed chromatin and binucleated cells also have their frequencies increased when compared to an unexposed control group. The investigation of the molecular mechanisms associated with the PM organic extract showed cytotoxicity in human lung cell lines (A549) at concentrations ≥ 4 nM BaPeq. Using non-cytotoxic doses the extract was able to activate proteins involved in the DNA damage response pathway (Chk1 and p53). Moreover, the specific contribution of the four most representative PAHs in the cashew nut roasting sample showed that benzo[a]pyrene was the most efficient to activate Chk1 and p53. Finally, the organic extract was able to increase persistently the mRNA expression involved in the PAHs metabolism (CYP1A1 and CYP1B1), inflammatory response (IL-8 and TNF-α) and cell cycle arrest (CDKN1A) for DNA repair (DDB2). The high PM concentrations and its biological effects associated warn of the serious harmful effects of artisanal cashew nut roasting and urgent actions should be taken to the sustainable development of this activity.

Desenvolvimento e caracterização de um sabonete contendo borras de café

Desde da antiguidade que o ser humano se preocupa com a sua aparência externa, em especial com a pele. Para além do desenvolvimento de cosméticos, surgiram também produtos mais complexos, os cosmecêuticos, que diferem dos cosméticos devido a poderem influenciar a função biológica da pele, causando modificações positivas e duráveis. O conceito de sustentabilidade é usado para definir ações e atividades humanas que visam suprir as necessidades atuais dos seres humanos, sem comprometer o futuro das próximas gerações. Ou seja, a sustentabilidade está diretamente relacionada ao desenvolvimento económico e material sem agredir o meio ambiente, utilizando os recursos naturais de forma inteligente para que eles se mantenham no futuro. Seguindo estes parâmetros, a humanidade pode garantir o desenvolvimento sustentável. As borras de café são consideradas como um subproduto alimentar, sem grande reutilização, o que promove danos no impacto ambiental. Por outro lado, as borras de café podem exercer grandes benefícios para a pele, pois são consideradas excelentes exfoliantes naturais com propriedades refirmantes. Os produtos à base de cafeína são aliados no combate à celulite, na estimulação da regeneração celular e da circulação sanguínea, bem como, no rejuvenescimento e revitalização da pele. Este trabalho consistiu no desenvolvimento de um sabonete, contendo borras de café, como forma de reaproveitamento de um subproduto alimentar rico em cafeína, com o intuito de obter produtos com boas propriedades cosméticas e elevada estabilidade física e química. As borras de café foram analisadas em termos da sua estabilidade física e química através de ensaios de estabilidade acelerada por centrifugação, textura, reologia e doseamento do teor de cafeína por HPLC. Os resultados obtidos através do controlo físico-químico dos sabonetes, da determinação do potencial irritante cutâneo e da análise sensorial efectuada em voluntários humanos, demonstraram que é possível preparar sabonetes de borra de café com boa estabilidade físico-química, boa tolerância cutânea e com características sensoriais adequadas, utilizando uma base de sabão constituída pelos ingredientes (INCI): Sodium Palmate, Sodium Palm Kernelate, Aqua (water), Glycerine, Fragância de café, Sodium Chloride, Butyrospermum Parkii Butter (Shea Butter), CI 778911 (Titanium Dioxide), Tetrasodium EDTA, CI 77499, Linalool e à qual foi adicionada 5% de borras de café.

Queijo minas padrão com reduzido teor de sódio: composição e caracterização sensorial

Sodium is an essential nutrient with important functions in the organism, however, its ingestion in excess may cause various health problems such as arterial hypertension, brain diseases, heart failure and chronic renal failure. In this context, the present study proposes to prepare Minas Padrão cheese with different contents of sodium with the objective of evaluating the effect of the addition of potassium chloride in sensory characteristics and hysicochemical properties, as well as in the proximal composition and in microbiological quality. The cheeses were elaborate in concentrations of 100% of NaCl (C), 80% of NaCl + 20% of KCl (T1), 60% of NaCl + 40% of KCl (T2), 40% of NaCl + 60% of KCl (T3) and 20% of NaCl + 80% of KCl (T4) and stored for 20 days at 10 ºC. The proximal composition and physicochemical was based on the determination of moisture content, fat, protein, ash, chloride, sodium, potassium, titratable acidity and pH of all treatments after 20 days of storage. The microbiological quality of the samples was monitored through the count of Total Coliforms and Escherichia coli, Staphylococcus aureus, Salmonella spp., mold and yeast in the first and fifteenth day of storage. The sensorial characterization was performed by the technique of Free Profile choice. The results showed that the replacement of sodium chloride by potassium in the Minas Padrão cheese in concentration higher than 40% presented significantly higher moisture contents. Cheese with a reduction greater than 60% of sodium obtained significantly effect in the titratable acidity, presenting higher values compared to the other treatments. The cheese with 20% of salt replacement did not differ statistically in relation to the control. When the proportion of substituent was increased, a significant reduction of the sodium content of up to 73% was observed. As the sodium was replaced by potassium in cheese, the potassium content increased significantly, stablishing a reduction of 82% in relation to the control. There was no effect to sodium substitution by potassium in fat, protein, ash and chlorides, as well as the pH values. The microbiological results were in accordance with the current legislation, therefore suitable to be eaten. According to the Free Profile Choice technique it was observed that the control C cheese (100% of NaCl) showed results very close to the other treatments, differing only in flavor attributes. The replacement of sodium by potassium in proportions of 20% contributed to a bitter taste detected by the tasters. Whereas, the appearance, flavor and texture attributes showed no significant differences compared to the Minas Padrão cheese.

Amidos crioulos: caracterização fundamental e influência de biopolímeros nas propriedades funcionais do amido

O trabalho apresentado nesta tese focou-se no estudo do amido, nomeadamente na avaliação das características físico-químicas, morfológicas, térmicas e reológicas do amido de seis variedades de milho crioulo, preservadas no estado de Santa Catarina (Brasil), com o intuito de contribuir para a valorização e preservação de variedades locais que são cultivadas em sistemas de produção orgânica, também conhecidas como variedades crioulas. Estas sementes são importantes quer para a preservação da biodiversidade quer para os pequenos produtores que as conservam e as produzem fazendo uso de uma agricultura sustentável e independente comercialmente. Para além da caracterização dos amidos crioulos foram também analisadas as alterações que ocorrem nos processos de gelatinização e retrogradação do amido quando realizados na presença de outros biopolímeros, nomeadamente a quitosana e galactomananas. No Capítulo I é apresentada uma breve revisão do conhecimento científico sobre o amido e sobre a quitosana e galactomananas, os outros biopolímeros utilizados. Igualmente é feita uma sucinta abordagem sobre as principais técnicas analíticas que foram utilizadas: reologia fundamental, calorimetria diferencial de varrimento, microscopia eletrónica de varrimento e espectroscopia de infravermelho médio. No capítulo II apresenta-se o isolamento dos amidos das seis variedades de milho crioulo e a sua caracterização junto com um amido comercial usado como modelo de comparação. Os amidos apresentaram genericamente características físicoquímicas semelhantes e o amido extraído das variedades crioulas MT e MPA 01 apresentaram menor temperatura de gelatinização e maior percentagem de retrogradação, respetivamente. Os efeitos da adição da quitosana e de três galactomananas (goma guar, goma de alfarroba e goma cassia) em sistemas mistos com o amido são analisados nos Capítulos III e IV respetivamente. A adição dos biopolímeros aos amidos resultou no aumento das temperaturas de gelatinização, na alteração da retrogradação do amido pelas galactomananas e na alteração das propriedades viscoeláticas dos géis formados. Os dados de infravermelho esclareceram que nos sistemas com quitosana, o amido formou complexos com o ácido acético usado para dissolver a quitosana e que esta por sua vez formou acetato de quitosana. O comportamento durante a gelatinização do amido comercial quando comparado com o amido do milho crioulo MPA na sua interação com as galactomananas é diferenciado.

Desenvolvimento e caracterização do queijo Santo Giorno, típico do sudoeste do Paraná, produzido com leite cru e fermento endógeno

Two cheese formulations made from raw milk and endogenous yeasts with 30, 60 and 180 days of maturation in two dairy Paraná Southwest were studied to evaluate their quality through physical, physical-chemical, microbiological and sensorial characteristics, as one of the stages of development of a typical regional cheese. The production was accompanied from designing the flowchart processing, where the samples were collected to perform the analysis of proteins, lipids, moisture, ash, carbohydrates, total solids, fat in dry matter, calories; water activity, instrumental texture (hardness, adhesiveness, springiness, cohesiveness, resiliency and chewiness), instrumental color (CIE Lab); microbiological quality was assessed searching for total and thermotolerant coliforms, coagulase positive staphylococci and Salmonella spp.; the acceptance related to sensory characteristics of color, appearance, flavor, texture, taste and purchase intent was evaluated through the structured hedonic scale. This research contributed information relevant to the production process, such as the realization of the viability in freeze-drying lactic acid bacteria yeast isolated from milk in the Southwestern Mesoregion of Parana and the results of the analysis of the cheese showed similarity between formulations, regarding the physical, physical-chemical characterization, moreover good microbiological quality, where the differences between samples of dairy products were not perceived by sensory panelists. Adjustments in standardization related to technological quality control is an extremely important factor for the success of dairy companies and small producers involved in the project and that they have the option of producing the Santo Giorno, a fine cheese, with the great advantage of adding features of region, with high standard of sanitary conditions and with great consumer acceptance of indicative.

Desenvolvimento e caracterização de micropartículas de amido reticuladas com agente fosfatado e avaliação da adsorção do azul de metileno

Starch has properties that make it one of the most studied biopolymers today. It is biodegradable, biocompatible, stable and non-toxic. This work has synthesis of starch and tapioca microparticles, through chemical modification by crosslinking with sodium tripolyphosphate agent in concentrations 7.5 and 15% (m / m). The amylose content was measured for starch and commercial cassava starch at 21.8% and 28.6%, respectively. According to the solubility index, processing in basic medium does not change the solubility of the material, but the addition of crosslinking agent increases this index, which changed from 12.8% for the control unprocessed, to 22.4% for the A5R15 sample. Soluble starch-based materials had a significant increase in the crosslinking density by increasing the concentration of crosslinker, from 1.4 in A5R7,5 sample, to 1.9 in A5R15. The cassava starch-based materials exhibited an opposite behavior: to increase the concentration of crosslinker crosslinking density decreased significantly in F5R7.5 from 2.9, to 1.9 in F5R15 sample. The point of zero charge (PZC) shows that below pH 4 the surface is positively charged. The surface area data is between 3,04 and 1,15 m2.g-1. The pore volume between 2.94 and 1.33 cm3.g-1 and pore size around 1.5 nm. The SEM indicates uneven distribution of microparticles, which are smooth, with no ridges. The maximum adsorption capacity of the materials were tested at pH 7.7 and for A5R15 and CA sample, at pH 2, 5, 6 and 9. It is noted that the processing in basic medium reduces the adsorption capacity of CA and CF in respect fo A and F. The adsorption in A5R15 sample has great dependency on the pH, reaching a value of 587 μg.g-1 in pH 7.7. The samples A5R15 and F5R7,5 adsorbed similar amounts, according to the statistical analysis, and significantly higher than their respective controls and showed lower desorption, indicating that the modification process was effective to control the release of methylene blue. The infrared spectra not show the characteristic bands of the phosphate bonds to the material formed, however, developments in hydroxyl characteristic band suggest modification in the way this group was linked after the reaction. After adsorption, the infrared spectra show different format in the band of hydroxyl. PCA analysis shows that the greatest changes observed in the IR spectra are observed in the region of 3500 cm-1. Thermal analysis showed three thermal events related to dehydration and material degradation. It is observed that the processing increases the temperature to the first mass loss, fixed at 12%, but not observed increased stability due to the presence of crosslinker or process.

Estudo das propriedades físico-químicas e avaliação de compostos bioativos em camarinhas ('Corema album' L.D. Don)

As camarinhas ('Corema album' L. D. Don) são pequenos frutos selvagens que se desenvolvem em arbustos dunares ao longo das costas da Península Ibérica. Apesar de serem ainda pouco conhecidas, as camarinhas são pequenos frutos que podem pertencer ao vasto grupo dos frutos vermelhos, vulgarmente conhecidos pelos seus efeitos benéficos na saúde. Desta forma, neste estudo foram realizadas várias análises às camarinhas no que respeita a propriedades de natureza física e química e em particular a alguns compostos com efeitos bioativos. Com a realização deste trabalho pretendeu-se avaliar as propriedades físico-químicas das camarinhas, bem como dos compostos bioativos com potenciais benefícios para a saúde. Nesse sentido, as bagas de camarinha foram avaliadas quanto às suas propriedades físicas (dimensões, peso, cor e textura), propriedades químicas (humidade, acidez, ºBrix, fibra, açúcares totais, açúcares redutores e vitamina C) e propriedades fenólicas (compostos fenólicos totais, orto-difenóis, flavonóides, taninos e atividade antioxidante, por DPPH e ABTS), em diferentes extratos de amostras de polpas e de grainhas liofilizadas. Os primeiros extratos ainda foram submetidos a uma simulações das condições do trato digestivo, para avaliar a bioacessibilidade dos compostos fenólicos e da atividade antioxidante. Este trabalho teve ainda como objetivo conhecer a bioacessibilidade dos compostos fenólicos totais e da sua atividade antioxidante, através do método da simulação “in vitro” das diferentes etapas do trato gastrointestinal. No que diz respeito às propriedades físicas analisadas, as camarinhas frescas demonstraram uma altura média de 8,6 mm, um diâmetro médio de 9,4 mm e uma massa média de 0,7 g. Relativamente à caraterização da cor, estas apresentavam uma cor clara (L*=79,8). Quanto à textura apresentaram alguma elasticidade média (2,9 mm) e uma baixa dureza (1,9 N). Nas análises químicas as camarinhas revelaram ser compostas, maioritariamente, por água (87,9%), por açúcares totais e fibras. Para além disso, apresentavam um teor em sólidos solúveis totais de 6,3 ºBrix, uma acidez de 1,4 g ácido tartárico/100 g e um teor de vitamina C de 2,8 mg de ácido ascórbico/100 g.Na quantificação dos compostos fenólicos totais e flavonóides, os extratos de acetona:água das amostras de polpas de camarinha branca apresentaram os valores mais elevados, 1614,1 mg EAG/100 g e 143,7 mg EQ/100 g, respetivamente. Relativamente à quantificação dos orto-difenóis e dos taninos os extratos de metanol e de acetona:água das amostras de grainhas de camarinha branca registaram os valores de 23,4 mg EAG/100 g e 915,7 mg/100 g, respetivamente. Na atividade antioxidante por DPPH e ABTS os extratos de acetona:água das amostras de polpas de camarinha branca apresentaram, respetivamente, os valores de 40,1 µmol ET/g e de 79,6 µmol ET/g. Na avaliação da bioacessibilidade verificou-se que ocorreu uma maior percentagem de compostos fenólicos disponíveis para absorção e uma maior preservação da sua atividade antioxidante nos extratos das grainhas, comparativamente aos extratos das polpas. Com este estudo concluiu-se que as camarinhas são pequenos frutos portadores de um grande potencial em diversos compostos bioativos benéficos para a saúde dos consumidores.