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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.

The overall objective of the work described in this Dissertation was to develop and verify a general reaction and diffusion model for non-catalytic reactions between gases and porous solids, particularly those relevant to the clean use of fossil fuels. Here, the internal pore structure of the solid was characterised by observing the kinetics in a regime limited only by intrinsic chemical reaction. It was hypothesised that a simple arbitrary function, f(X), determined from experimental measurements of rate vs. conversion in a kinetically-controlled regime, could be used in place of formal, mathematical pore models, to describe the evolution of pore structure during a reaction influenced by intraparticle mass transfer. The approach was used to study (i) the gasification of chars by CO2, where the only product was gaseous, (ii) the calcination of CaCO3 cycled between calcined and carbonated states, where the products were a gas and a solid, and (iii) the sulphation of virgin and sintered CaO by SO2, the only product being solid. Studies of calcination showed that, at least for limestones subjected to a history of cycling between the calcined and carbonated states, a correctly-determined f(X) could be applied to different sizes of particles at temperatures different to that at which f(X) was determined. Somewhat surprisingly, it was found that the f(X) determined from one, cycled, limestone was successful in predicting the conversion of other cycled limestones of different geological origin. It was concluded that the process of cycling between the calcined and carbonated states at the same process condition had significantly reduced the differences apparent in the pore structures of the different limestones when first calcined from the virgin materials. The experimentally-observed effects of pressure, concentration of CO2 and temperature described in the literature were explained successfully by the mathematical model. Finally, the study of sulphation explained satisfactorily (i) the reason for there being a maximum in the ultimate conversion of CaO to CaSO4 at a specific temperature, and (ii) the processes controlling the overall uptake of SO2 by sintered CaO, such as might be produced from a calcium-looping cycle for capturing CO2 from flue gases. For both the virgin and the cycled calcines, the ultimate conversion to CaSO4 seemed to be limited by the pore volume below 300 nm diameter. Two mechanisms were identified to explain why CaO cannot be fully sulphated to CaSO4. In summary, this work has demonstrated the applicability of the general reaction and diffusion model to gasification, calcination and sulphation reactions, and verified the f(X) approach for describing pore evolution during reaction.

Potential new ore deposits containing significant levels of enargite, a copper arsenic sulphide mineral, are being considered for development. The processing of high arsenic copper concentrates directly in copper smelters is difficult due to environmental concerns. This thesis investigates a process using sulphation roasting as an alternative method for processing enargite concentrates; copper is recovered from the calcine by acid leaching, gold is extracted from the leach residue by conventional cyanidation and arsenic is either fixed in the calcine or precipitated from process emissions. In this research, sulphation roasting between the temperatures of 300-800oC, with varying oxygen and sulphur dioxide partial pressures, was investigated. Experiments indicated that high levels of copper extraction, as well as arsenic fixation, could be achieved from the produced calcines through hydrometallurgical processes. At operating temperatures between 400-550oC copper sulphate, copper arsenate, iron sulphate, hematite and iron arsenate form in the calcine, as well as some arsenic being volatilized as arsenic trioxide. At processing temperatures between 475-575oC, greater than 80% of the arsenic was retained in the calcine as copper and iron arsenates. Copper arsenate would be weak-acid soluble and fixed in an effluent treatment plant along with arsenic captured in the wet-gas scrubber bleed solution. As operating temperatures increase above 650oC copper sulphates were converted into oxysulphates, oxides and ferrites, hematite production was favoured, and arsenic was primarily volatilized. Increasing the sulphur dioxide addition in the reaction atmosphere resulted in additional sulphate formation and increased sulphate stability at higher temperatures. Sulphation roaster heat balances were developed for calcines produced at two temperatures, 500 and 750oC. They indicated that while high copper extraction and arsenic fixation rates could be achieved, the sulphation roasting reactions are highly exothermic and significant cooling water would need to be added. Due to these issues, it is likely that partial roasting operations would be economically favourable in greenfield operations. However, niche applications of this process in operations with existing copper SX/EW facilities in good acid markets, have the potential to be economically favourable. / Thesis (Master, Mining Engineering) -- Queen's University, 2012-08-17 20:14:36.292

Η εμπειρία έχει δείξει ότι στα αυτόνομα φωτοβολταϊκά συστήματα, η μπαταρία είναι το πιο αδύναμο στοιχείο αφού το προσδόκιμο ζωής της είναι συνήθως αρκετά μικρότερο από ότι όλων των άλλων στοιχείων του συστήματος και για το λόγο αυτό είναι και το πιο ακριβό στοιχείο με το 30% ή και περισσότερο του κόστους ενός αυτόνομου φωτοβολταϊκού συστήματος καθ’όλη τη διάρκεια της ζωής του να οφείλεται στο σύστημα αποθήκευσης. Αντικείμενο αυτής της εργασίας είναι η μελέτη των προβλημάτων που αντιμετωπίζουν οι μπαταρίες μολύβδου οξέος (που είναι ο βασικός τύπος μπαταριών που χρησιμοποιείται για την αποθήκευση στα φωτοβολταϊκά συστήματα) και οι τρόποι αντιμετώπισής τους με σκοπό αφενός την επέκταση της διάρκειας της χρήσιμης ζωής των μπαταριών αυτών και αφετέρου τη μείωση του κόστους συντήρησης και αντικατάστασής τους. Ιδιαίτερη βαρύτητα δίνεται στο πρόβλημα της θειίκωσης, το οποίο έχει αποδειχθεί ο σημαντικότερος παράγοντας γήρανσης και τελικά καταστροφής της πλειοψηφίας των μπαταριών μολύβδου οξέος που χρησιμοποιούνται στα φωτοβολταϊκά συστήματα και παρουσιάζονται τεχνικές που μπορούν να χρησιμοποιηθούν για την πρόληψη και την αντιμετώπιση του πολύ σοβαρού αυτού προβλήματος. / Experience has shown that in stand alone photovoltaic systems, battery is the weakest element since its expected lifetime is usually considerably smaller than those of other elements. Thus its cost is the most expensive with 30% or above of the total cost of stand alone photovoltaic system throughout its whole lifespan. Subject of this dissertation is the study of problems that lead acid batteries face and the way to treat them. The aim is to extend their useful lifetime and the reduction of the cost of maintenance and replacement. The problem of sulphation is given special importance, since it has been proved that it constitutes the main aging factor for the majority of lead acid batteries used in photovoltaic systems. Suggestions for treatment are given.

The thesis is focused on remitting lead-acid segments of partial charge mode which simulates the conditions in HEV. The experimental cells were submitted to different pressures on the electrode system. The main aim of the thesis was to minimize the irreversible sulphating of the negative electrodes, which are in the PSoC regime limiting in the overall life of lead-acid accumulators. All cells were submitted to measurement of the negative electrode potentials, resistance of active materials, contact resistance of the grid – the active material and measurements of pressure changes during three PSoC cycles.

La partie oligosaccharidique des glycoconjugués, présents à la surface des cellules eucaryotes, intervient dans de nombreux processus biologiques de reconnaissance et d'adhésion cellulaire. L'essor de la glycobiologie au cours des vingt dernières années a permis de définir, à partir de l'implication de ces structures glycaniques, de nombreuses applications thérapeutiques potentielles. Cependant la fabrication de nouveaux médicaments à partir d'oligosaccharidiques requiert leur disponibilité en grande quantité mais leurs obtentions par purification ou par méthode de synthèse chimique et enzymatique restent difficiles et couteuses et donnent un rendement faible. Le laboratoire CERMAV a récemment développé une technologie cellulaire, non polluante, capable de produire rapidement et en grande quantité un certain nombre d'oligosaccharides d'intérêt biologique. Le procédé baptisé « usine cellulaire » repose sur la co-expression de glycosyltransférases recombinantes chez la bactérie Escherichia coli. La sulfatation des glycanes est un élément important de leurs propriétés biologiques. Celle-ci dépend de l'activité de sulfotransférases, dont l'activité chez Escherichia coli a été peu étudiée. Par contre, ces enzymes utilisent des accepteurs oligosaccharidiques dont la synthèse est maîtrisée par le procédé d'usine cellulaire. Nous avons exprimé des gènes de sulfotransférases afin de permettre in vivo la sulfatation d'accepteurs oligosaccharidiques endogènes produits dans la bactérie. Les familles de molécules synthétisées dériveront des motifs GlcAlac, Lacto-N-néotétraose, et LewisX dont la synthèse in vivo est maîtrisée. Nous avons également réalisé une synthèse combinée chimio-enzymatique d'une néoglycoprotéine porteuse d'un analogue de l'épitope HNK-1, déterminant sulfaté impliqué notamment dans la régénération des motoneurones. Finalement nous avons entrepris une étude préliminaire d'adaptation du procédé d'« usine cellulaire » à la synthèse de glycanes sulfatés chez Saccharomyces cerevisiae. / The oligosaccharide moety of glycoconjugates, present on the eukaryotic cell surface, is involved in many biological processes of recognition and cell adhesion. The rise of glycobiology over the last twenty years has helped to define, from the involvement of these glycan structures, many potential therapeutic applications. However, the manufacture of new drugs from oligosaccharide requires their availability in large quantities but their varieties by purification or by method of chemical and enzymatic synthesis remain difficult and expensive and lead to low yield. CERMAV has recently developed a clean and fast cell technology, which is able of producing large quantities of several oligosaccharides of biological interest. The process called "cell factory" is based on the co-expression of recombinant glycosyltransferases in Escherichia coli. Sulfation of glycans is an important part of their biological properties and depends on the activity of sulfotransferase, whose activity in Escherichia coli has not been well studied. But these enzymes use oligosaccharide acceptor whose synthesis is controlled by the process of cell factory. We expressed genes of sulfotransferase to allow the in vivo sulfation of endogenous oligosaccharide acceptor produced in the bacterium. Families of molecules synthesized drift patterns of GlcAlac, Lacto-N-neotetraose, and Lewisx whose synthesis in vivo is controlled. We also performed a combined chemo-enzymatic synthesis of a neoglycoprotein bearing an analogue of the epitope HNK-1, involved particularly in the regeneration of motoneurons. Finally we tried to adapt the method of "cell factory” for the synthesis of sulfated glycans in a eukaryotic organism such as yeast Saccharomyces cerevisiae.

This work deals with lead-acid batteries operating in hybrid electric vehicles mode, i.e. in a partial state of charge. The adverse effects such as premature capacity loss and large internal resistance can markedly affect the life of a lead battery. The experiment described in this work aims to clarify the influence of the titanium dioxide in the active mass of negative electrodes especially in the life of lead acid batteries.