No description available.

L'ochratoxine A (OTA) est un métabolite secondaire produit par des espèces appartenant aux genres Aspergillus et Penicillium qui a été liée à certaines conditions avec des effets néphrotoxiques, immunotoxiques, tératogènes et cancérogènes. La présence d'OTA dans le café vert a été détectée depuis 1974 et sa transmission à la boisson a été mise en évidence en 1989. La torréfaction du café est un procédé thermique qui peut avoir un effet sur la teneur en OTA, avant 1988, on pensait que l'OTA était détruite pendant la torréfaction, mais après plusieurs chercher sont des résultats contradictoires publiés dans % de réduction (de 0 à 100%). Plusieurs auteurs émis les hypothèses suivantes pour expliquer cette réduction : Isomérisation de la toxine dans la position C3 formant un diastéréoisomère moins toxique (Studer-Rohr et al, 1995 et Bruinink et al, 1997), protection de la dégradation d’OTA par l'humidité du grain (Boudra et al 1995; Blanc et al, 1998 et Stegen et al, 2001.), existence de réactions avec le café toxine parent ou réarrangements de la molécule OTA à températures de torréfaction (Suarez-Quiroz et al, 2005). Une autre étude sur la dégradation thermique de OTA pure a montré la formation de deux composés moins toxiques, 14-(R)-ochratoxine A et de la 14-descarboxi-ochratoxine A (Cramer et al, 2008). Parce qu'il n'y a pas de données concluantes sur l'effet de la torréfaction sur l'OTA dans le grain et le besoin de bases scientifiques pour établir des règles pour l'exportation de café vert, l'objectif de ce travail était d'étudier l'impact des différents types de torréfaction sur la stabilité thermique de l'OTA dans le café et l'élucidation chimique des produits de transformation. Deux niveaux de contamination ont été obtenus à partir de café contaminés artificiellement par Aspergillus westerdijkiae (5,3 et 57,2 ppb d'OTA). Ces lots sont grillés à 230° en utilisant deux méthodes : La torréfaction à tambour (TR) et à lit fluidisé (LF). Les échantillons ont été prélevés toutes les 3 min pour TR et chaque min 0,9 pour LF pour quantifier la valeur résiduelle d¡¯OTA. Les résultats ont montré que le procédé de torréfaction par TR (plus lent) était plus efficace que la FL dans l'élimination de l'OTA (67% et 36%, respectivement, pour une torréfaction moyenne). Nous avons déterminé le taux de dégradation thermique de OTA pure et de l'OTA mélangée avec les composants du café (5 sucres, 3 acides aminés, la caféine et les acides chlorogéniques), montrant que les interactions se déroulent en fonction des conditions de pH et de pKa des composants testés, dans ce cas, en influant sur la réactivité et la vitesse de dégradation de l'OTA. Un produit de transformation (PT) a été observé sur les chromatogrammes obtenus à partir de l'interaction de l'OTA avec les composants du café. Des tests d'alcalinisation et de chauffage de OTA pure ont confirmé que le PT provient de la modification structurale de la molécule d'OTA et n’est pas un produit de l'interaction avec les composants naturels du café. L'effet du pH et de la température sur l'extraction de l'OTA dans le café contaminé a été testé dans ce travail, les résultats ont montré une plus grande extraction de la toxine à un pH de 8,5 et 6°. Au même pH à 20° il y avait une plus importante formation d'un produit de transformation. Le PT a été purifié pour mener à bien sa caractérisation chimique. La nature chimique du produit de transformation, les données spectroscopiques telles que celles obtenus sous UV-Vis (max: 237nm), l'affinité avec la phase mobile de l'OTA, l'analyse de l'alcalinisation (phénomène de régénération de l'OTA et PT), l'analyse d’isotopes stables (SIDA’s) et le spectre de masse (ion moléculaire M+1: 420 m/z), suggèrent que la structure de le PT d'OTA durant le processus de torréfaction correspond à un analogue de l'OTA qui conserve son groupe carboxyle acide et conformément à la fragmentation correspond à la Hydroxy-ochratoxine A (OH-OTA), avec des quantités mineures d’ OTA et de ses isomères. / Ochratoxin A (OTA) is a secondary metabolite produced by species belonging to the genera Aspergillus and Penicillium and this toxin has been associated with certain illnesses within nephrotoxic effects, immunotoxic, teratogenic and carcinogenic. The presence of OTA in green coffee was detected in 1974 and its transmission into the beverage was made evident in 1989. Roasting coffee is a thermal process that have an effect on the OTA content. Before 1988 it was thought that the OTA was destroyed during roasting, but after several investigations, results published are contradictory results published in the % reduction (from 0 to 100%). Several authors have established hypothesis that try explain this reduction: Isomerization of the toxin in the C3 position forming a less toxic diastereomers (Studer-Rohr et al., 1995 and Bruinink et al., 1997), Protection of grain moisture degradation OTA (Boudra et al., 1995; Blanc et al., 1998 and Stegen et al., 2001), Existence of reactions with the parent toxin coffee or rearrangements of the OTA molecule roasting temperatures (200¡ã and 250¡ãC) (Su¨¢rez-Quiroz et al., 2005). Another study on thermal degradation of pure OTA showed the formation of two less toxic compounds 14 - (R)-ochratoxin A and the 14-descarboxi-Ochratoxin A (Cramer et al., 2008).Because there are no conclusive data regarding the effect of roasting on OTA in grain and the need for scientific bases for establishing regulations for export of green coffee, the objective of this work was to study the impact of different types of roasting on the thermal stability of OTA in coffee and chemical elucidation of the transformation products.Two levels of contamination were obtained by the contamination of coffee with a strain of A. westerdijkiae (5.3 and 57.2 ppb of OTA). These lots were roasted at 230 ¡ã C using two methods: Drum rotation (TR) and fluidized bed (LF). Samples were taken every 3 min from TR and every 0.9 min for LF to quantify the residual OTA. The results showed that in roasting process by TR (slower), it was more effective than with LF in the elimination of OTA (67% and 36%, respectively, for a medium roast). The thermal degradation rate of pure OTA and of OTA mixed with the components of coffee (5 sugars, 3 amino acids, caffeine and chlorogenic acids), were determined, showing that interactions took place dependent themselves on the conditions of pH and pKa values of the components tested, in this case by influencing by the reactivity and the rate of degradation of OTA. A transformation product (TP) was observed in the chromatograms obtained from the interaction of OTA with the components of coffee. A test of alkalinization and warming of pure OTA confirmed that the TP comes from the structural modification of the OTA molecule and is not a product of interaction with the natural components of coffee. The pH and temperature showed an effect in extraction of OTA in contaminated coffee, the results show better extraction of the toxin at pH 8.5 at 60 ¡ãC. At the same pH at 20 ¡ãC, it was shown a greater formation of the transformation product.The TP was purified to carry out its chemical characterization. The chemical nature of compound transformation and spectroscopic data such as UV-Vis (¦Ëmax: 237nm), the affinity with the mobile phase of the OTA, the analysis of alkalinization (OTA regeneration phenomenon and TP) analysis of stable isotopes (SIDA's) and the mass spectrum (molecular ion M +: 420 m / z), suggest that structurally the TP of OTA during the roasting process corresponds to an analogue of OTA which retains its acidic carboxyl group and in accordance to fragmentation corresponds to the Hydroxi- Ochratoxin A (OH-OTA), as well as minor amounts of OTA and its isomers.

No description available.

No description available.

Fumes emitted from coffee bean roasters contain various chemicals such as aldehydes, pyridine, volatile fatty acids, and ketones. These chemicals have high odor intensities and are sensitive to human breathing organs and eyes. In Taiwan, most of these fumes are not well controlled before venting to the atmosphere. This research attempted to eliminate these odorous and offensive chemicals by chemical scrubbing methods. Sodium hypochlorite oxidation followed by hydrogen peroxide reduction (hypochlorite-peroxide) was investigated first. After that, ozone oxidation followed by hydrogen peroxide reduction (ozone-peroxide) was also tried. In both methods, hydrogen peroxide acted as a reducing agent for the elimination of either residual chlorine or ozone emitted from the oxidation reaction. Experimental results indicated that both methods were effective. An oxidative scrubbing liquid with an initial effective chlorine content of 200 mg/L and a pH of 12, and an reducing scrubbing liquid with an initial hydrogen peroxide concentration of 1% and a pH of 12 could remove an average of 85% of total hydrogen carbons (THC) in the fume gas from a coffee bean roaster. With a dose of 10 ppm ozone in the fume gas to the oxidative scrubbing liquid (water only) followed by an reducing scrubbing liquid with an initial hydrogen peroxide concentration of 0.3% and a pH of 12, an average removal of 80% of the THC could be removed. An odor intensity (expressed by the dilution to threshold ratio) of 9,772 in the original fume could be reduced to as low as 31 by both methods. As indicated by the data from GC/MS (gas chromatography-mass spectrometry) analysis for the hypochlorite-peroxide method, acrolein, vinyl acetate, 2-butanone, and acetone in the roaster fume could almost completely be eliminated. Traces of chlorinated hydrocarbons as potential secondary pollutants were detected in the treated gases from the hypochlorite-peroxide scrubbing system. While by the ozone-peroxide one, satisfactory results were also obtained with no chlorinated hydrocarbons emitted. An economical analysis shows that the ozone-peroxide approach is a practical one for actual control applications.

The sulphation and sulphate decomposition occurring during the oxidation of nickel concentrates were studied by thermal analysis. Samples of industrial nickel concentrates were heated in inert gas to temperatures between 400°C and 850°C and oxidized isothermally in air or in a 4%O2-96%N2 mixture. During isothermal oxidation of the concentrates, SO2 evolved from the roasting reactions led to partial formation of metal sulphates. Following the oxidation and sulphation of the sample, the decomposition of the formed sulphates was studied. This was completed either by heating the sulphated sample to 950°C to thermally decompose the sulphates, or by lowering the partial pressure of oxygen while holding the sample at the isothermal oxidation temperature. The sulphation of the sample was found to follow the parabolic rate law, implying diffusion as the rate controlling-step. The thermal decomposition of the sulphates occurred at a near constant rate, implying zero-order kinetics.

The sulphation and sulphate decomposition occurring during the oxidation of nickel concentrates were studied by thermal analysis. Samples of industrial nickel concentrates were heated in inert gas to temperatures between 400°C and 850°C and oxidized isothermally in air or in a 4%O2-96%N2 mixture. During isothermal oxidation of the concentrates, SO2 evolved from the roasting reactions led to partial formation of metal sulphates. Following the oxidation and sulphation of the sample, the decomposition of the formed sulphates was studied. This was completed either by heating the sulphated sample to 950°C to thermally decompose the sulphates, or by lowering the partial pressure of oxygen while holding the sample at the isothermal oxidation temperature. The sulphation of the sample was found to follow the parabolic rate law, implying diffusion as the rate controlling-step. The thermal decomposition of the sulphates occurred at a near constant rate, implying zero-order kinetics.

Abstract Increasing efficiency is a necessary target for an industrial roaster nowadays. This thesis presents some studies on efficiency improvement in the zinc roasting process - process characterisation, control design, implementation and testing. The thesis focuses on the roaster, i.e. on research regarding the phenomena in the roaster furnace. By learning more about the roasting mechanism, particle size growth and dynamics of the furnace, new control implementations have been developed. More measurements, analyses and calculated variables have been added to give more information on the state of the furnace. New control variables have been introduced to give the operators more opportunities to set the conditions so that they are more suitable for the actual concentrate feed mixture. Equipment modifications have also been done. In this research, both laboratory and plant experiments have been performed together with thermodynamic evaluations and calculations. It has been necessary to make plant trials in order to obtain information about the impacts of different variables on the process. Only full-scale experiments give reliable results of the behaviour of an industrial furnace. The experiments with the roaster furnace have emphasised the study of both the metallurgy and the dynamics of the roasting process. The on-line calculated oxygen coefficient and its active control have proved important. The particle size distribution analysis of the furnace calcine has been shown to be a significant source of information for evaluating the state of the roasting furnace. The main target is to improve the economic performance. The key is to be able to be flexible in using different kinds of raw materials, because the main income is the treatment charge. The trend is that concentrates are becoming finer, which increases the challenges for roaster furnace control. The capability to use low-grade concentrates is also a major challenge and improves the economic result. Research and development on the boiler and mercury removal has also been part of this work for many reasons. Improved boiler performance and mercury removal gives more freedom in choosing concentrates and operating the roaster furnace. The approach has been the same as in the roaster furnace research and development work. Control improvements based on existing knowledge, such as fuzzy control systems for controlling the furnace temperature and mercury removal, did stabilize the process, but they did not solve all the problems regarding process stability. The research and development concept of this thesis has provided the extra knowledge needed for further improvement of process control. The results of the process characterisation have led to the implementation of a new and effective control strategy. The research and development carried out has improved performance in a number of ways: increased running time of the furnace and boiler, in-depth knowledge of roasting phenomena which led to new control methods and instructions for the operators, improved quality of sulphuric acid and a method to control its quality, measurements and analyses that give valuable information of the state of the process – all of which are now in use. In the future, the emphasis will be placed on the research and development of roaster furnace performance, which will be a great challenge. Control of the roaster furnace is the key to the economic success of the roasting process and more information about these phenomena is needed for improving and optimising control.

Selective oxidation and sulfation roasting of nickel concentrate followed by leaching was investigated as a novel route for nickel production. In the oxidation roasting stage, the iron species in the nickel concentrate was preferentially oxidized to form iron oxides, leaving non-ferrous metals (Ni, Cu, Co) as sulfides. The roasted product was then sulfation roasted to convert the sulfides of the latter metals into water-soluble sulfates. The sulfates were then leached into solution for further recovery and separation from iron oxides. The oxidation of nickel concentrate was firstly studied by means of thermogravimetric and differential thermal analysis over a wide temperature range. A reaction scheme was deduced, in which preferential oxidation of iron sulfide species occurred over a wide temperature range up to about 700 ºC, forming a Ni1-xS core with iron oxide shell. A batch fluidized bed roaster was then constructed to study the oxidation and sulfation roasting of nickel sulfide concentrate. Oxidation roasting tests were carried out at temperatures between 650 °C and 775 °C. It was found that low temperatures (e.g. 650 °C) are favorable for the preferential oxidation of iron sulfide species while minimizing the formation of nickeliferous oxides, i.e. trevorite and NiO. Several parameters were varied in the sulfation roasting experiments, including the sulfation gas flowrate, sulfation roasting temperature, the addition of Na2SO4, sulfation roasting time, and the oxidation roasting temperature. Under optimized conditions of sulfation gas composition (95% air, 5% SO2), temperature (700 °C), Na2SO4 addition (10 wt%) and time (150 min), the conversions to sulfates were 79% Ni, 91% Cu, and 91% Co. Only 5% Fe forms water-soluble sulfate. The residue from the leaching of calcine in water contained 49% Fe and 10% Ni, which is a suitable feedstock for the production of ferronickel alloys. Therefore, further studies were also conducted to evaluate the reduction behavior of the residue with CO, H2 and graphite.

[pt] Concentrado minerais sulfetados são uma importante fonte de matérias-primas nos processos de extração de metais não-ferrosos. No que diz respeito ao cobre, estes são usualmente processados segundo um fluxograma contemplando as etapas de ustulação, fusão mática, conversão e refino. Todavia, algumas características dos concentrados podem limitar a sua aceitação nas plantas de processamento tais como: baixo teor de cobre assim como a presença de elementos ditos deletérios, como, por exemplo, o flúor e seus efeitos corrosivos sobre materiais refratários após a transformação e ácido fluorídrico; ainda que o material possua um teor do metal de interesse elevado. Dentro desse contexto, o presente trabalho tem por objetivo avaliar o processamento químico de concentrados sulfetados de cobre com essas características a fim de entender o seu comportamento nos processos de ustulação, visando à identificação de condições que minimizem os efeitos danosos do flúor, no caso de concentrados de alto, assim como determinar uma janela operacional que possibilite a obtenção seletiva de CuSO4, no caso de concentrados de baixo teor. Para atender a esses objetivos, foi levado a efeito um estudo teórico incluindo uma breve revisão da literatura e uma apreciação termodinâmica das reações químicas mais relevantes em cada sistema reacional. O estudo experimental foi conduzido através da avaliação do efeito de variáveis específicas para cada sistema reacional. No caso particular de concentrados de alto teor contendo flúor, os experimentos contemplaram a presença, ou não, de água na atmosfera reacional ao passo que nos ensaios envolvendo concentrados de baixo teor de cobre foram levados a efeito variando a temperatura e a composição química da atmosfera reacional a partir da recirculação de parte dos produtos gasosos, como, por exemplo, o SO2. Os materiais envolvidos foram caracterizados por meio de microscopia eletrônica de varredura e difração de raios-x. As previsões teóricas de ambos os sistemas reacionais puderam ser confirmadas na caracterização dos produtos reacionais obtidos após o processamento químico dos concentrados sulfetados de alto e baixo teor de cobre. No que tange o primeiro destes, observou-se que o flúor tende a permanecer estável na forma de fluorita quando na ausência de umidade no sistema reacional. Por outro lado, no que diz respeito ao último destes materiais, verificou-se que o reciclo de parte dos produtos gasosos do processo é responsável por uma melhora de desempenho da reação química de ustulação visando à formação seletiva de sulfato de cobre e óxido de ferro. / [en] Sulfide minerals concentrates are an important source of raw materials for non-ferrous metals extraction processes. For copper, these are usually processed through a flowchart containing the operations of roasting, matte smelting, conversion and refining. However, some concentrates characteristics may limit its acceptance in processing plants such as low copper content and the presence of deleterious elements, such as fluorine and its corrosive effects as result of its transformation into hydrofluoric acid; even if the metal content is this material is high. Within this context, this study aims to evaluate the chemical processing of sulfide concentrates with these characteristics in order to understand their roasting behavior, in order to identify conditions that minimize the fluorine harmful effects for concentrate with high copper content, and determine an operating window that allows the selective obtainment of CuSO4, for low grade concentrates. To meet these objectives, it was carried out a theoretical study including a brief review of the literature and a thermodynamics assessment of the most important chemical reactions in each reaction system. The experimental study was conducted evaluating the effect of specific variables for each reaction system. In the case of concentrates of high grade containing fluorine, the experiments contemplate the presence or absence of water in the reaction atmosphere while the tests involving the concentrate with low copper content were carried out by varying the temperature and the chemical composition of the atmosphere, recirculating part of the gaseous products, like SO2. The materials were characterized by scanning electron microscopy and x-ray diffraction. The theoretical predictions of both reaction systems could be confirmed in the characterization of the reaction products obtained after the chemical processing of sulfide concentrates of high and low copper content. In what touches the former, it was observed that fluorine tends to remain stable as fluorite in the absence of moisture within the reaction system. On the other hand, regarding the latter material, it was found that the part of recycled gaseous products of the process are responsible for a performance improvement of the roasting reaction focused on the selective formation of copper sulfate and iron oxide.