Estudo da remediação de um aquífero contaminado com sulfato e metais através de barreira reativa permeável orgânica.

Este trabalho teve como objetivo geral estudar a viabilidade técnica de utilizar bagaço de cana como meio reativo de barreiras reativas permeáveis (BRP) para remoção de sulfato e metais de águas subterrâneas contaminadas. O estudo baseou-se em investigação experimental, por meio de ensaios laboratoriais de coluna, e em modelagem matemática, para a qual utilizaram-se também alguns dados obtidos em um estudo de caso de uma unidade industrial contaminada com sulfato e metais. Neste local contaminado, as características hidrogeológicas e topográficas propiciam a utilização de uma barreira reativa permeável como técnica de remediação. Barreiras reativas permeáveis são uma alternativa para remediação de águas subterrâneas que vem progredindo rapidamente na última década, a partir de ensaios de bancada e coluna em laboratório para implementação em escala real em campo. Três colunas bióticas foram montadas utilizando bagaço de cana como meio reativo e um material de base poroso constituído de areia e cascalho para fornecer adequada condutividade hidráulica, com a proporção de 1:28 em massa seca. Também foi adicionado ao meio reativo um inóculo bacteriano composto por esterco bovino dissolvido. Uma quarta coluna, sem inóculo e contendo um agente biocida, compôs o experimento branco (abiótico). Uma solução sintética foi introduzida nas colunas simulando condições da água subterrânea do estudo de caso, com velocidade de Darcy em torno de 2,0x10-7 m/s composta por sulfato e metais (zinco e níquel) com concentrações de 6.000 mg/L e 15 mg/L, respectivamente. Os resultados das análises da fase líquida das colunas bióticas apresentaram: (i) média da taxa de remoção de sulfato durante todo o tempo do experimento de 49 mg/L/dia; (ii) as concentrações de Zn e Ni diminuíram de 15 mg/L para valores não detectáveis pela técnica analítica utilizada (< 0,01 mg/L); (iii) aumento do pH de 5.5-5.8 para valores entre 6,8-8,0; (iv) redução do valor do potencial de óxido redução (Eh) para valores de até -200mV. Não foram observadas reduções das concentrações de metais e sulfato na fase líquida da coluna abiótica e os valores de pH e Eh permaneceram dentro das faixas iniciais. Análises nas fases sólidas das colunas bióticas por MEV e EDS após o término do experimento identificaram a presença de Ni, Zn, S e Mn, indicando a precipitação desses metais em forma de sulfetos. Estes elementos não foram detectados na fase sólida da coluna abiótica. Assim, pôde-se inferir que toda a remoção de sulfato verificada nas colunas bióticas pode ser atribuída a redução bacteriana de sulfato. A partir das condições experimentais dos ensaios, foi realizada a modelagem e o dimensionamento da BRP. Para a estimativa da cinética de redução de sulfato, aplicou-se a solução analítica de Van Genuchten para transporte de contaminantes com degradação, obtendo-se uma taxa de decaimento de primeira ordem de 0,01 dia-1. A determinação da espessura e tempo de residência da barreira foi realizada considerando que a concentração de sulfato na saída da barreira fosse menor ou igual a 250 mg/L. O resultado do dimensionamento de uma BRP preenchida com bagaço de cana e areia nas proporções de 1:28 em massa seca resultaria em uma BRP de 7,1 m de espessura, com tempo de residência de 950 dias, no local de estudo de caso. Caso fosse utilizado o dobro da proporção de bagaço de cana e areia em massa seca (1:14), a implantação da BRP apresentar-se-ia viável, com espessura aproximada de 4 m. Através destes resultados, pôde ser comprovada a hipótese de que bagaço de cana como substrato e esterco bovino como inóculo compõem um meio reativo viável para a redução de sulfato e precipitação de metais em uma BRP.

Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

Study of the thermal decomposition of petrochemical sludge in a pilot plant reactor

The pyrolysis of a sludge produced in the waste water treatment plant of an oil refinery was studied in a pilot plant reactor provided with a system for condensation of semivolatile matter. The study comprises experiments at 350, 400, 470 and 530 °C in nitrogen atmosphere. Analysis of all the products obtained (gases, liquids and chars) are presented, with a thermogravimetric study of the char produced and analysis of main components of the liquid. In the temperature range studied, the composition of the gas fraction does not appreciably vary. In the liquids, the light hidrocarbon yield increases with increasing temperature, whereas the aromatic compounds diminish. The decomposition of the solid fraction has been analysed, finding a material that reacts rapidly with oxygen regardless of the conditions it is formed.

Surface, Thermal and Antimicrobial Release Properties of Plasma-Treated Zein Films

The effects of dielectric barrier discharge plasma treatment on zein film containing thymol as an active ingredient were evaluated. The plasma discharge was optically characterized to identify the reactive species. A significant increase in the film roughness (p < 0.05) was observed due to the etching effect of DBD plasma, which was correlated with the increase in the diffusion rate of thymol in the food simulant. The diffusion of thymol from the zein film was measured in aqueous solution. The kinetics of thymol release followed the Fick’s law of diffusion as shown by the high correlation coefficients between experimental and theoretical data. No significant change (p > 0.05) was observed for the thermal properties of the antimicrobial films after DBD plasma treatment.

Behavior of different soot combustion catalysts under NOx/O2. Importance of the catalyst–soot contact

Four different catalysts (Pt/Al2O3, Ce0.8Zr0.2O2, PrO2−x and SrTiCuO3) have been investigated on a laboratory scale to evaluate their potential as diesel soot combustion catalysts under different experimental conditions, which simulate the situation found in a continuous regeneration technology trap (dual-bed configuration of catalyst and soot) or a catalyst-coated filter system (single-bed configuration, both catalyst and soot particles mixed under loose-contact mode). Under dual-bed configuration, the behavior of the catalysts towards soot combustion are very similar, despite the differences observed in the NO2 production profiles. However, under single-bed configuration, there are important differences in the soot combustion activities and in the NO2 slip profiles. The configurations chosen have an enormous impact on CO/(CO + CO2) ratios of combustion products as well. The most active catalyst under NOx + O2 is PrO2−x combining a high contribution of active oxygen-assisted soot combustion as well as high NO2 production activity along the catalytic bed.

Thermal decomposition of the different particles size fractions of almond shells and olive stones. Thermal behaviour changes due to the milling processes

The aim of this study is to investigate the effect of particle size on the non-isothermal pyrolysis of almond shells (AS) and olive stones (OS) and to show possible differences in the composition of the different fractions obtained after milling and sieving. The results obtained from the study of different particle size of AS and OS samples show significant differences in the solid residue obtained and in the shape and overlapping degree of the peaks, especially with the smaller particle size. These differences can be due to different factors: (a) the amount of inorganic matter, which increases as particle size decreases, (b) heat and mass transfer processes, (c) different sample composition as a consequence of the milling process which may provoke changes in the structure and the segregation of the components (in addition to the ashes) increasingly changes the composition of the sample as the particle size decreases.

Catalytic performance of CuO/Ce0.8Zr0.2O2 loaded onto SiC-DPF in NOx-assisted combustion of diesel soot

This work presents a comparative study between the catalytic performance of the 2% CuO/ceria-zirconia powder catalyst and the same catalyst supported on silicon carbide DPF (Diesel Particulate Filter) towards NO oxidation reaction and soot combustion reaction. The ceria-zirconia catalyst was prepared by the co-precipitation method and 2 wt% copper was incorporated by the incipient wetness impregnation method. The catalyst was incorporated onto the ceramic support using a simple and organic solvent-free procedure by a simply dipping the DPF into an aqueous solution of the catalyst. The powder catalyst has been characterized using N2 adsorption at −196 °C, XRD and Raman Spectroscopy; whereas the catalytic coating morphology has been evaluated by SEM and the mechanical stability by an adherence test. Both catalyst configurations were tested for NO oxidation to NO2 and for soot combustion under NOx/O2. The results revealed that incorporation of the very active copper/ceria-zirconia catalyst onto SiC-DPF has been successfully achieved by a simple coating procedure. Furthermore, the catalytic coating has shown suitable mechanical, chemical and thermal stability. A satisfactory catalytic performance of the catalytic-coated filter was reached towards the NO oxidation reaction. Moreover, it was proved that the catalytic coating is stable and the corresponding coated DPF can be reused for several cycles of NO oxidation without a significant decrease in its activity. Finally, it was verified that the loose-contact mode is a good choice to simulate the catalytic performance of this active phase in a real diesel particulate filter.

The combined effect of plastics and food waste accelerates the thermal decomposition of refuse-derived fuels and fuel blends

Mechanical treatments such as shredding or extrusion are applied to municipal solid wastes (MSW) to produce refuse-derived fuels (RDF). In this way, a waste fraction (mainly composed by food waste) is removed and the quality of the fuel is improved. In this research, simultaneous thermal analysis (STA) was used to investigate how different mechanical treatments applied to MSW influence the composition and combustion behaviour of fuel blends produced by combining MSW or RDF with wood in different ratios. Shredding and screening resulted in a more efficient mechanical treatment than extrusion to reduce the chlorine content in a fuel, which would improve its quality. This study revealed that when plastics and food waste are combined in the fuel matrix, the thermal decomposition of the fuels are accelerated. The combination of MSW or RDF and woody materials in a fuel blend has a positive impact on its decomposition.

Semivolatile and Volatile Compound Evolution during Pyrolysis and Combustion of Colombian Coffee Husk

Thermal characterization of coffee husk (Coffea arabica) from Colombian coffee has been studied. Different products, mostly volatile and semivolatile compounds, were analyzed, paying special attention to 16 polycyclic aromatic hydrocarbons (PAHs) classified by the United States Environmental Protection Agency (U.S. EPA) as priority pollutants, frequently used for checking toxicity in environmental samples. A fixed amount of raw material was exposed to different excess air ratios (λ = 0–2.33) and nominal temperature of 1123 K in a horizontal quartz reactor. The results show that coffee husk is a promising biomass for energetic exploitation with reduced formation of PAHs in a low air excess ratio. This implies reduction of carcinogenic potential in the limited presence of oxygen, demonstrated by calculating the carcinogenic potential (KE) for each experimental condition. Most volatile and semivolatile compounds followed different trends, with the oxygen presence prevailing their decomposition with increasing the air excess ratio.

Pollutant emissions during the pyrolysis and combustion of flexible polyurethane foam

Thermal decomposition of flexible polyurethane foam (FPUF) was studied under nitrogen and air atmospheres at 550 °C and 850 °C using a laboratory scale reactor to analyse the evolved products. Ammonia, hydrogen cyanide and nitrile compounds were obtained in high yields in pyrolysis at the lower temperature, whereas at 850 °C polycyclic aromatic hydrocarbons (PAHs) and other semivolatile compounds, especially compounds containing nitrogen (benzonitrile, aniline, quinolone and indene) were the most abundant products. Different behaviour was observed in the evolution of polychlorodibenzo-p-dioxins and furans (PCDD/Fs) at 550 °C and 850 °C. At 550 °C, the less chlorinated congeners, mainly PCDF, were more abundant. Contrarily, at 850 °C the most chlorinated PCDD were dominant. In addition, the total yields of PCDD/Fs in the pyrolysis and combustion runs at 850 °C were low and quite similar.

Thermal model for charring rate calculation in wooden cellular slabs under fire

Wood is a natural and traditional building material, as popular today as ever, and presents advantages. Physically, wood is strong and stiff, but compared with other materials like steel is light and flexible. Wood material can absorb sound very effectively and it is a relatively good heat insulator. But dry wood burns quite easily and produces a great deal of heat energy. The main disadvantage is the high level of combustion when exposed to fire, where the point at which it catches fire is from 200–400°C. After fire exposure, is need to determine if the charred wooden structures are safe for future use. Design methods require the use of computer modelling to predict the fire exposure and the capacity of structures to resist those action. Also, large or small scale experimental tests are necessary to calibrate and verify the numerical models. The thermal model is essential for wood structures exposed to fire, because predicts the charring rate as a function of fire exposure. The charring rate calculation of most structural wood elements allows simple calculations, but is more complicated for situations where the fire exposure is non-standard and in wood elements protected with other materials. In this work, the authors present different case studies using numerical models, that will help professionals analysing woods elements and the type of information needed to decide whether the charred structures are adequate or not to use. Different thermal models representing wooden cellular slabs, used in building construction for ceiling or flooring compartments, will be analysed and submitted to different fire scenarios (with the standard fire curve exposure). The same numerical models, considering insulation material inside the wooden cellular slabs, will be tested to compare and determine the fire time resistance and the charring rate calculation.

Single-pulse shock tube studies of the kinetics of the reaction N + O [arrow right over arrow left (reversible reaction)] 2 NO between 2000-3000⁰ K,

At head of title: Combustion Dynamics Division, Air Force Office of Scientific Research, ARDC, Washington, D. C., File no. AF 18(600)-1332.

Investigation of chemical kinetics phenomena in rocket engines.

"Unclassified."

Thermal characterization of polyester-melamine coating matrices prepared under nonisothermal conditions

Thermal analysis methods (differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis) were used to characterize the nature of polyester-melamine coating matrices prepared under nonisothermal, high-temperature, rapid-cure conditions. The results were interpreted in terms of the formation of two interpenetrating networks with different glass-transition temperatures (a cocondensed polyester-melamine network and a self-condensed melamine-melamine network), a phenomenon not generally seen in chemically similar, isothermally cured matrices. The self-condensed network manifested at high melamine levels, but the relative concentrations of the two networks were critically dependent on the cure conditions. The optimal cure (defined in terms of the attainment of a peak metal temperature) was achieved at different oven temperatures and different oven dwell times, and so the actual energy absorbed varied over a wide range. Careful control of the energy absorption, by the selection of appropriate cure conditions, controlled the relative concentrations of the two networks and, therefore, the flexibility and hardness of the resultant coatings. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Cbem 41: 1603-1621, 2003.

Degradation of azo-dye Orange II by a photoassisted Fenton reaction using a novel composite of iron oxide and silicate nanoparticles as a catalyst

A novel nanocomposite of iron oxide and silicate, prepared through a reaction between a solution of iron salt and a dispersion of Laponite clay, was used as a catalyst for the photoassisted Fenton degradation of azo-dye Orange II. This catalyst is much cheaper than the Nafion-based catalysts, and our results illustrate that it can significantly accelerate the degradation of Orange II under the irradiation of UV light (lambda = 254 nm). An advantage of the catalyst is its long-term stability that was confirmed through using the catalyst for multiple runs in the degradation of Orange II. The effects of the H2O2 molar concentration, solution pH, wavelength and power of the LTV light, catalyst loading, and initial Orange II concentration on the degradation of Orange 11 were studied in detail. In addition, it was also found that discoloration of Orange 11 undergoes a faster kinetics than mineralization of Orange II and 75% total organic carbons of 0.1 mM Orange II can be eliminated after 90 min in the presence of 1.0 g of Fe-nanocomposite/L, 4.8 mM H2O2, and 1 x 8W UVC.