Thesis (MBA)--Stellenbosch University, 2005. / ENGLISH ABSTRACT: South Africa's main requirements for power are in the form of electricity and liquid fuels The country's electricity is generated mainly from coal while the liquid fuels requirement is mainly from crude oil. Both coal and crude oil use are coming under increasing pressure locally because of pollution and accompanying environmental awareness. Internationally both energy sources are also increasingly being abandoned as preferred energy sources, in first world countries, in favour of cleaner energy sources.ln view of these developments in the macro environment South Africa's gas to liquids refinery built in the early 1990's seems a well placed past investment ahead of its time. This study project looks at the economic feasibility of the continued existence of the PetroSA gas to liquid plant in Mossel Bay.The study looks at South Africa as well as Southern Africa's energy resources , the effect of changing legislation on the future use of energy resources and the economics of the Mossel Bay facility. The study finds that South Africa's abundance of coal reserves, its lack of oil and gas reserves and the slow pace of environmental legislation delivery means that gas is unlikely to become a major source of energy in South Africa.The Mossel Bay gas to liquids plant is profitable but its high fixed costs and certain growth of this cost component means that the continued feasibility of operations is dependant on favourable movements in the exchange rate and oil price. To answer the question about whether to continue operating or close down the analysis found that although although early closure would provide a return of more than 15 percent it would be even more viable financially to make an investment for more gas and continue operations.The main reason for the better than average projected returns is the high oil price .The decision to close down the Mossel Bay plant is not likely to be based on financial considerations alone. The recommendation is thus to continue operations untill 2016.The investment required to secure more gas would , even in the worst case scenario, provide a satisfactory return on investment. / AFRIKAANSE OPSOMMING: Suid Afrika se energie behoeftes is hoofsaaklik vir elektrisiteit en brandstof. Die meerderheid van die land se elektristeit word deur middel van steenkool opgewek terwyl ru-olie gebruik word om brandstof te vervaardig. Beide steenkool en ru-olie word al hoe meer onder druk geplaas as gevolg van besoedeling en 'n meer omgewing bewuste publiek. Op internasionale vlak , in eerste wereld lande word die gebruik van steenkool en ru-olie al hoe meer afgeskaf ten gunsle van skoner kragbronne. In die lig van hierdie verwikkeling in die makro omgewing mag dit op die oog af Iyk of PetroSA se gas na vloeistof aanleg in Mosselbaai, wat reeds in die vroee 1990's gebou is, as 'n goeie destydse strategiese belegging voorkom. Hierdie studie projek ondersoek die ekonomiese lewensvatbaarheid van die voorgesette bestaan van die PetroSA se Mosselbaai gas na vloeislof aanleg. Die studie kyk na Suid-Afrika sowel as die groter Suider Afrika se natuurlike energiebronne, die invloed van verandering in wetgewing op die toekomstige gebruik van energiebronne en die ekonomiese kenmerke van die aanleg in Mosselbaai. Die bevinding van die studie is dat Suid-Afrika se oorvloed van steenkool, sy tekort aan natuurlike gas en die stadige pas waarteen omgewings-wetgewing ontwikkel word, daartoe lei dat gas nie 'n volmatige energiebron in Suid Afrika sal word nie. Die aanleg in Mosselbaai is huidiglik winsgewind maar sy hoe vastekoste en groei hiervan belemmer sy vooruitsigte vanuit 'n finansiele oogpunt. Die winsgewindheid van die aanleg is afhanklik van 'n verswakkende Suid Afrikaanse geldeenheid en verhogende ru-olie pryse. Die vraag onstaan dus of die aanleg moet toemaak en of produksie moet voortgaan. Die ondersoek vind dat alhoewel die sluiting van die aanleg 'n opbrengs van meer as 15 persent sal lewer dit selfs meer finansieel aantreklik is on te belê in meer gas sodat produksie kan voortgaan. Die hoofrede vir die bogemiddelde opbrengs is die hoe oilieprys. Dit is onwaarskynlik dat die oorweging om die Mosselbaaise aanleg sluit suiwer op finansieele oorwegings sal rus. Die aanbeveling is dus om voort te gaan met produksie tot 2016. Die belegging wat nodig is vir meer gas sal selfs onder die mees pessimistiese omstandighede steeds 'n bevredigende opbrengs lewer.

Cette recherche, fondée sur une enquête de terrain et l’analyse d’archives, vise à comprendre l’histoire et la mise en tourisme des complexes industriels dédiés au sucre ainsi que leur intégration au patrimoine culturel taiwanais. Après une présentation des origines du sucre et de son implantation, nous traiterons de l’histoire économique de l’île de façon chronologique, afin de mieux cerner le contexte de création puis de fermeture des complexes industriels. Puis, en retraçant l’histoire de l’architecture moderne et de l’urbanisme au Japon et dans ses colonies, nous expliquerons quelle a été l’organisation spatiale et l’architecture des sites, conçus comme des modèles avancés de communautés industrielles modernes. Un tour d’horizon des vestiges présents et des éléments disparus permettra de faire un état des lieux du niveau de préservation du patrimoine industriel taiwanais et de découvrir que si certains édifices sont encore en parfait état, d’autres ont parfois subi des destructions ou de lourdes modifications architecturales après 1945. Enfin, le détail de la mise en tourisme des sites à l’heure actuelle nous renseignera d’une part sur les projets de réutilisation décidés pour faire vivre les anciens complexes industriels maintenant transformés en « parcs culturels » et la façon dont les Taiwanais souhaitent mettre en valeur ce patrimoine redécouvert progressivement à partir des années 1990. D’autre part, nous découvrirons quels discours ont été choisi (et par qui) lors de la présentation de l’histoire des sites et de la mémoire ouvrière, dans le contexte sous-jacent de conflits interethniques et politiques intenses que connaît Taiwan depuis plusieurs décennies. / This research, based on a field study and on archives analysis, aims to understand the history and the transition into touristic spots of industrial complexes dedicated to sugar as well as their integration into the Taiwanese cultural heritage. After presenting the origins of sugar and it’s implantation in Taiwan, we will address the island’s economical history in a chronological manner in order to better understand the context in which these industrial complexes were created and later closed. Then, by recounting the history of modern architecture and urbanism in Japan and Japanese colonies, we will explain the spatial and architectural organization of these sites, built as advanced models of modern industrial communities. An overview of the present remains and of the elements that are now gone will enable us to highlight the Taiwanese heritage’s current state of preservation. Furthermore, to point out that even though some buildings are still in perfect condition, others have undergone destruction or heavy architectural modifications after 1945. Finally, detailing of the current transition into touristic venues of these sites will inform us, on one hand, on the projects dedicated to bringing back to life old industrial complexes by transforming them into « cultural parks » and, on the other hand, on the way the Taiwanese want to showcase a heritage they have rediscovered starting in the early nineties. Furthermore, we will bring to light what kind of discourses have been chosen (and by whom), when the history of these sites and their working class memory are presented, in Taiwan’s underlying context of intense inter-ethnic and political conflicts of the past few decades.

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

A stable mixed culture, deposited as ATCC 55644, previously shown to degrade petroleum hydrocarbons at relatively high concentrations was used as the source of inoculum. This culture was grown in Stanier’s minimal media, either in the presence of different concentrations of naphthalene, nitrobenzene and toluene (NNT) or naphthalene and toluene (NT) as the sole source of C and/or N. Results showed that the majority of the strains isolated from the mixed culture were able to grow in the presence of NNT or NT. A total of 20 different isolates were isolated from the mixed culture. Individual isolates were grown in Stanier’s minimal medium containing a single hydrocarbon as the source of carbon or carbon and nitrogen. Only one strain was found to grow solely in the presence of nitrobenzene as the source of C and N. Most of the other isolates were able to grow in the presence of naphthalene, toluene, acenaphthene, anthracene, fluoranthene and phenanthrene, n-dodecane, hexadecane, n-pentadecane, n-tetradecane, and n-octadecane. Planktonic and immobilized cells of the controlled mixed culture (ATCC 55644) were grown in separate Sequential Batch Reactors (SBR) using Stanier's media, to which naphthalene, nitrobenzene and toluene were added as the sole source of C and/or N. Biodegradation was determined by measuring the residual hydrocarbon in the SBR and the amount of trapped volatile organic carbon (VOC) and the evolved CO2. Gas chromatography data showed that immobilized cells were able to degrade NNT faster than the planktonic cells. This observation was confirmed by CO2 evolution. Over time the loading of hydrocarbon was significantly increased from a starting level of 400 ppm (Naphthalene), 100 ppm (Nitrobenzene), and 500 ppm (toluene), to a final level of 3000 ppm (Naphthalene), 400 ppm (Nitrobenzene), and 1600 ppm (toluene). While increasing nutrient loading, the frequency of re-feeding with hydrocarbons was changed from an initial re-feeding every 60 hrs to a final re-feeding frequency of 18 hrs. The experiments clearly showed that the attached, mixed microbial community was able to effectively and rapidly degrade high concentrations of hydrocarbons. This demonstrated the practical advantages of employing attached, mixed microbial cultures in a SBR.

This thesis examines sulfide oxidation in 4 physically and mineralogically diverse acid sulfate soil (ASS) materials collected from coastal floodplain sites in north-eastern New South Wales. The aim of this study is to gain further understanding of the process of sulfide oxidation in ASS materials, which will allow improved and more effective management strategies to be applied to these materials. The process of sulfide oxidation was examined using laboratory incubation experiments. The oxidation of pyrite was the primary cause of initial acidification of the ASS materials studied. Although the acid volatile sulfur fraction increased in concentration by an order of magnitude over the initial 8 days of incubation, the subsequent oxidation of this fraction did not result in substantial acidification. Sulfate (SO42-) was the dominant sulfur species produced from sulfide oxidation, however, water-soluble SO42- was a poor indicator of the extent of sulfide oxidation. The sulfoxyanion intermediates thiosulfate (S2O32-) and tetrathionate(S4O62-) were only detected in the early stages of incubation, and their relative abundance appeared to be pH dependent. The diminishing presence of these 2 sulfur species as oxidation progressed was indicative that ferric iron (Fe3+) and bacterial catalysis were driving the oxidation processes. The rate of sulfide oxidation, and consequent rate of acidification, was highly dependent on the soil pH and oxygen availability. Accelerated sulfide oxidation was only observed at low pH (i.e. pH < 4.0) when oxygen availability was not limited. The application of sub-optimal amounts of neutralising agents prevented severe soil acidification in the short-term (i.e. up to 2 months), but had little effect on decreasing the rate of sulfide oxidation and acidification in the long-term. Sub-optimal amounts of CaCO3 accelerated sulfide oxidation and acidification of the peaty marcasitic ASS material resulting in elevated soluble Fe and Al concentrations. For some of the ASS materials, sub-optimal applications of seawater-neutralised bauxite refinery residue (SNBRR) also resulted in elevated soluble Al concentrations. The response of partially-oxidised ASS materials to the exclusion of oxygen was variable. The rate of sulfide oxidation, acidification and the production of soluble oxidation products generally decreased markedly when subjected to anoxia. However, especially in highly acidic ASS materials (i.e. pH < 3.5), sulfide oxidation and acidification generally occurred (albeit at much slower rates), most probably due to oxidation by Fe3+. Rapid sulfide re-formation occurred in the peat ASS material that had been oxidised for 63 days, with 0.47% reduced inorganic sulfur (SCR) formed over 60 days of anoxia. Biogeochemical sulfide formation consumes acidity, however, sulfide re-formation was ineffective in reversing acidification under the conditions of this experiment. The peroxide oxidation methods examined were method dependent and substantially underestimated peroxide oxidisable sulfur, sulfidic acidity and net acidity. The precipitation of jarosite during peroxide oxidation was a major factor contributing to the underestimation in these ASS materials. Clay mineral dissolution may contribute towards the underestimation of both sulfidic and net acidity using peroxide oxidation methods. The atmospheric loss of sulfur and acidity was also identified as a possible additional interference. This study has shown that the initial pH of an ASS material is a useful indicator (additional to those already used) of the potential environmental hazard of an ASS material when oxygen is expected to be non-limiting, such as when ASS materials are excavated and stockpiled. The recommended action criteria need to be reassessed as the data indicate that the current criteria are conservative for alkaline and neutral ASS materials, but should be lowered for all acidic ASS materials (i.e. pH < 5.5) to 0.03% sulfide regardless of texture. Alternative strategies are necessary for the management of ASS materials that are subject to oxidation when the addition of optimal rates of neutralising materials cannot be ensured. The treatment of sites containing actual ASS materials by management strategies that rely on oxygen exclusion need to be accompanied by strategies that include either acid neutralisation or containment in order to reduce acid export from the site. The peroxide oxidation methods examined were subject to substantial interferences, and consequently are unable to reliably provide accurate measurements of the reduced inorganic sulfur fraction, sulfidic acidity, and net acidity in ASS materials.

[pt] Esta dissertação investiga a aplicação de Algoritmos Genéticos e de Co-Evolução Cooperativa na otimização da programação da produção em refinarias de petróleo. Refinarias de petróleo constituem um dos mais importantes exemplos de plantas contínuas multiproduto, isto é, um sistema de processamento contínuo gerador de múltiplos produtos simultâneos. Uma refinaria, em geral, processa um ou mais tipos de petróleo, produzindo uma série de produtos derivados, como o GLP (gás liquefeito de petróleo), a nafta, o querosene e o óleo diesel. Trata- se de um problema complexo de otimização, devido ao número e diversidade de atividades existentes e diferentes objetivos. Além disso, neste problema, algumas atividades dependem de que outras atividades já tenham sido planejadas para que possam então ser planejadas. Um caso típico é o das retiradas de produtos de uma unidade de processo, que dependem de que a carga já tenha sido planejada, assim como em qual campanha a unidade estará naquele instante. Por isso, o uso de modelos revolucionários convencionais, como os baseados em ordem, pode gerar muitas soluções inválidas, que deverão ser posteriormente corrigidas ou descartadas, comprometendo o desempenho e a viabilidade do algoritmo. O objetivo do trabalho foi, então, desenvolver um modelo evolucionário para otimizar a programação da produção (scheduling), segundo objetivos bem definidos, capaz de lidar com as restrições do problema, gerando apenas soluções viáveis. O trabalho consistiu em três etapas principais: um estudo sobre o refino de petróleo e a programação da produção em refinarias; a definição de um modelo usando algoritmos genéticos e co-evolução cooperativa para otimização da programação da produção e a implementação de uma ferramenta para estudo de caso. O estudo sobre o refino e a programação da produção envolveu o levantamento das várias etapas do processamento do petróleo em uma refinaria, desde o seu recebimento, destilação e transformação em diversos produtos acabados, que são então enviados a seus respectivos destinos. Neste estudo, também foi levantada a estrutura de tomada de decisão em uma refinaria e seus vários níveis, diferenciando os objetivos destes níveis e explicitando o papel da programação da produção nesta estrutura. A partir daí, foram estudadas em detalhes todas as atividades que normalmente ocorrem na refinaria e que são definidas na programação, e seus papéis na produção da refinaria. A decisão de quando e com que recursos executar estas atividades é o resultado final da programação e, portanto, a saída principal do algoritmo. A modelagem do algoritmo genético consistiu inicialmente em um estudo de representações utilizadas para problemas de scheduling. O modelo coevolucionário adotado considera a decomposição do problema em duas partes e,portanto, emprega duas populações com responsabilidades diferentes: uma é responsável por indicar quando uma atividade deve ser planejada e a outra é responsável por indicar com quais recursos essa mesma atividade deve ser realizada. A primeira população teve sua representação baseada em um modelo usado para problemas do tipo Dial-A-Ride (Moon et al, 2002), que utiliza um grafo para indicar à função de avaliação a ordem na qual o planejamento deve ser construído. Esta representação foi elaborada desta forma para que fosse levada em conta a existência de restrições de precedência (atividades que devem ser planejadas antes de outras), e assim não fossem geradas soluções inválidas pelo algoritmo. A segunda população, que se responsabiliza pela alocação dos recursos para a execução das atividades, conta com uma representação onde os operadores genéticos podem atuar na ordem de escolha dos recursos que podem realizar cada uma das atividades. Finalmente, des / [en] This work investigates the use of Genetic Algorithms and Cooperative Coevolution in refinery scheduling optimization. Oil refineries are one of the most important examples of multiproduct continuous plants, that is, a continuous processing system that generates a number of products simultaneously. A refinery processes various crude oil types and produces a wide range of products, including LPG (liquefied petroleum gas), gasoline, kerosene and diesel. It is a complex optimization problem, mainly due to the number of different tasks involved and different objective criteria. In addition, some of the tasks have precedence constraints that require other tasks to be scheduled first. For example, in order to schedule a task that transfers one of the yields of a certain crude distillation unit, both the task that feeds the crude oil into the unit and the task that sets the unit`s current operation mode must already be scheduled. Therefore, applying traditional evolutionary models, like the order- based ones, can create many infeasible solutions that will have to be corrected or rejected later on, thereby jeopardizing the algorithm performance and feasibility. The main goal was the development an evolutionary model satisfying well-defined objectives, which would optimize production scheduling and address the various constraints entailed in the problem, thus generating only feasible solutions. This work consisted on three main steps: a survey on crude oil refining and refinery scheduling; the development of a cooperative coevolutionary model to optimize the refinery scheduling and the development of a software tool for case studies. The study about refining and scheduling involved gathering information about the existent processes in a refinery, starting from the arrival of crude oil, its distillation and transformation into several products and, finally, the delivery of these products to their respective destination. The levels of decision making in a refinery were surveyed too, in order to identify the main goals for each one, and how the scheduling level fits into the structure as whole. Then, all the routine scheduling tasks and their roles in a refinery were carefully studied. The decision of when and how to assign those tasks is the final output of the scheduling task, so it must be the main output of the algorithm too. The development of the evolutionary model consisted of a survey on some of the most common evolutionary approaches to scheduling. The adopted coevolutionary model breaks the problem down into two parts, thus using two species with different responsibilities: One is responsible for deciding when a task should be scheduled, while the other is responsible for assigning a resource for this task. The first species representation was based on a model used for the Dial-a- Ride (Moon et al, 2002) kind of problems, and uses a graph to help the fitness evaluation function find the right order in which to schedule the tasks. This representation was devised in such a way that the precedence constraints were satisfied and no infeasible solutions were generated. The representation of the second species, which assigns resources for the tasks, let genetic operators change the selection order when picking a resource for a task. Finally, a software tool was developed to be used for implement this model and for performing a case study. This case study should comprise all the needed characteristics, in order to test the quality of the representation as well as evaluate the results. A simple refinery was designed, containing all equipment types, tasks and constraints found in a real-world refinery. The constraints mentioned are the precedence constraints, handled by the graph used by the first species, plus other operational constraints found in refinery scheduling. It was possible, then, to see the decoding of chromosomes into feasible solutions, always satisfying all the constraints. Several tests

La bioconversion des biomasses lignocellulosiques est actuellement un grand défi pour le développement de technologies de bio-raffinage. Le manque de connaissances des mécanismes de liquéfaction et de saccharification est l’un des principaux facteurs qui pénalisent le développement des procédés de bio-raffinage. Ce travail est centré sur le développement d’analyses physiques et biochimiques in-situ (viscosimétrie, focus beam reflectance measurement) et ex-situ (rhéometrie, granulométrie laser, morphogranulométrie, sédimentation…) pour améliorer la compréhension des mécanismes de déstructuration desfibres lignocellulosiques et caractériser les cinétiques de libération de carbone fermentescible. Des substrats modèles (cellulose microcristalline, papier Whatman) et industriels (pâte à papier, bagasse de canne à sucre) ont été utilisés avec différentes conditions d'hydrolyse (1% à 30%w/v, 0.1 à 0.5mL enzyme/ g cellulose). Les résultats obtenus ont permis:- de proposer et de valider les mesures in-situ de la viscosité de la suspension et de la distribution des longueurs de corde des particules, ainsi que sa conversion en distribution de diamètre.- de montrer l'impact de la nature et de la concentration de substrat et des ratios enzyme/substrat sur les évolutions des paramètres physico-biochimiques lors de l'hydrolyse. Ces effets ont été quantifiés sur les limitations de transfert.- d'établir un modèle phénoménologique de comportement rhéologique des suspensions initiales- de montrer que les cinétiques physico et bio-chimiques sont des cinétiques du second ordre- de montrer que, pour des hydrolyses à haute teneur en matière sèche, on peut réduire considérablement la limitation des transferts liée aux hautes concentrations et contrôler la cinétique de production de glucose par une stratégie d’ajouts cumulés desubstrat. / In the context of biofuels and chemicals production of petroleum substitutes from renewable carbon, bioconversion of lignocellulose biomasses is currently a major challenge. The limited knowledge of liquefaction and saccharification mechanisms stands as the main factor which penalizes bio-refinery progress. The present work is centred on the development of in-situ(viscosimetry, focus beam reflectance measurement) and ex-situ (rheometry, diffraction light scattered, morphometry, decantation…) physical and biochemical analysis to expand our understanding of the destructuration mechanisms of lignocellulose fibres and to characterise the release kinetics of fermentable cellulosic carbon. Model (microcrystalline cellulose,Whatman paper) and industrial (paper-pulp, sugarcane bagasse) lignocellulose matrices under a large range of hydrolysis conditions (1% up to 30%w/v and 0.1 up to 0.5mL enzyme/g cellulose) were studied during 24h hydrolysis experiments (pertinent period to appreciate transfer limitations). Our scientific results allow:- to propose and validate the in-situ measurements of the suspension viscosity and chord length distribution together with its conversion into particle size distribution.- to demonstrate the impact of the substrate nature and concentration and of the enzymatic ratios on the evolution of physical- and biochemical parameters during hydrolysis. Their impacts on transfer phenomena were quantified.- to establish phenomenological models for rheological behaviour of initial suspensions.- to describe all physical (viscosity, particle size) and biochemical (substrate and product) kinetics by second order reaction models.- to demonstrate that, for high dry matter concentration hydrolysis, a cumulative feeding substrate strategy allows considerably reducing the transfer limitations linked to high concentrations and to control the glucose production kinetics.

South Africa is a water scarce country. The expansion of the industrial, mining, and agricultural sectors to meet the needs of South Africa’s growing population requires more water. There is therefore an urgent need to develop effective wastewater treatment processes in order to recover and reuse water. This dissertation presents the treatment of an acidic wastewater stream from a platinum refinery which at present is being disposed of by contract with a waste disposal company. The major concern in treating the acid effluent stream is the high concentration of sodium ions (18 200 mg/l) and chloride ions (104 900 mg/l). The precipitation process is used to treat wastewater, but ultimately it generates more secondary waste as a sludge. The other process that is used to treat wastewater is reverse osmosis (RO). RO is usually preferred in the last stage of the treatment because the process is more expensive as membranes need to be replaced regularly. The approach used in this research focuses on evaporating liquid, consequently concentrating the remaining solution until the ions in the solution crystallize. The liquid produced is recycled back into the platinum plant for reuse, and the remaining salt crystals are collected as the useful product. The proposed water treatment process produces dilute hydrochloric acid as the condensate and a crystallized sodium chloride rich residue. The refinery is currently disposing of around 20 000 l/day of wastewater to landfills. The proposed treatment process can recover half of the volume of the wastewater stream to the refinery, helping reduce the fresh water consumption of the process by 10 000 l/day. Furthermore, this will reduce the volume of wastewater going to disposal by a half, namely only 10 000 l/day will need to be disposed of. The amount of Cl that can be recovered is variable and depends on the quantity of chloride in the wastewater. In the two samples processed the recovery was between a 2,5 w% and 10,7 wt% aqueous HCl solution. This corresponds to a saving of between 250 to 1000 kg/day of HCl. As the concentration of the recovered solution is variable, the recycling process would need to monitor the composition of the recycled stream and make up the acid concentration to some fixed value for reuse in the prices. The production of a dilute hydrochloric acid stream should be particularly attractive to the platinum refinery as the operation of the refinery requires hydrochloric acid as a feed. Thus, by recycling the wastewater, the refinery would reduce the volume of wastewater to be disposed of thereby reducing the cost of disposal of the waste while simultaneously reducing the cost of buying fresh hydrochloric acid. The proposed recovery of liquid and recycling it back to the refinery, will also reduce the environmental impact of the refinery, and very importantly in a water scarce country, reduce the freshwater consumption of the process. / Physics / M. Sc. (Physics)

At the end of 2016, the Swedish petroleum and biofuel company Preem applied for an environmental permit to convert high-sulfur bunker oil to low-sulfur petrol and diesel at Preemraff Lysekil. Something that required an expansion of the refinery. The process ended abruptly in September 2020 when Preem chose to withdraw their application. In connection with the process, two actor coalitions were formed, with one being for an expansion and the other against. Both coalitions had the explicit goal of reducing greenhouse gas emissions and preventing climate change. The difference, however, was their view on whether this could be achieved thanks to an expansion of Preemraff Lysekil, or if it could only happen without it. Through their actions the coalitions have tried to influence the policy process in a direction that is desirable for them. This study aims to systematically map the coalitions and their actions and contribute to a deeper understanding of their actions and impact on the process of the planned expansion project of Preemraff Lysekil. The study is designed as a qualitative case study and is based on The Advocacy Coalition Framework (ACF), which can be used to explain and understand beliefs and policy change when multiple actors are involved in a policy process. According to the ACF, actors who share similar policy core beliefs come together in coalitions to increase the chances of policy change. The study also uses urban regime theory to understand the informal and unspoken agenda between Preemraff Lysekil and Lysekil municipality. The results from previous research show several common denominators with the Preemraff Lysekil case. The analysis shows that the actors who were against an expansion had similar deep core beliefs and consistent policy core beliefs, they also had a consensus on how the policy change should be implemented. They have tried to influence the process by appealing court decisions and tried to get the Swedish government to take over the assessment of the application, which also happened. The analysis shows that the actors who were in favor of an expansion had more dispersed deep core beliefs but were consistent in their policy core beliefs and secondary beliefs. They have made attempts to stop the government from taking over the case from the court. As these attempts have been unsuccessful, they instead tried to get the government to allow an expansion. By using different forms of resources, both coalitions have tried to get the public and decision-makers to support their own proposal for policy change, with varying results. What ultimately led Preem to withdraw the application is not clarified. Maybe the pressure from those who were against an expansion became too powerful, maybe the COVID-19 pandemic left such a big mark on international production chains and the global market that an expansion was no longer profitable. There is also a possibility that Preem's decision is based on both parts, but we will probably never know.

Les régions de Midi-Pyrénées (France) et de Chongqing (Chine) sont riches en plantes aromatiques et médicinales dites oubliées (ou médiévales). Afin de valoriser pleinement les différentes bio-molécules extractibles de ces plantes, le concept de MAP-raffinerie a été créé et appliqué à une sélection de plantes issues de ces deux régions. Plusieurs technologies d’extraction utilisant l’eau comme solvant vert (hydrodistillation, distillation à la vapeur et extraction par eau sub-critique) ont ainsi été employées et leur impact tant sur la composition des huiles essentielles que sur la récupération des molécules anti-oxydantes a été évalué. Dans un premier temps, une liste de plantes aromatiques et médicinales oubliées, voire sous-utilisées dans les deux régions a été établie selon des règles de sélection prédéfinies. Six plantes modèles de la région de Midi-Pyrénées (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. et Spartium junceum L.) et trois plantes de la région de Chongqing (Tussilago farfara L., Citrus aurantium L. et Saussurea costus) ont finalement été retenues. Puis, le concept de MAP-raffinerie a été appliqué à ces plantes afin d’étudier leur possible valorisation globale. L’étude des compositions chimiques des extraits volatils des racines de Tussilago farfara L. et de Calendula arvensis L., ainsi que des boutons de fleurs de Spartium junceum L. a été réalisée par GC et GC-MS pour la première fois. Les principaux composés chimiques dans l’extrait volatil de racines de Tussilago farfara L. étaient des hydrocarbures sesquiterpéniques et des composés aliphatiques tandis que les principaux composés chimiques dans l’extrait volatil de racines de Calendula arvensis L. étaient des sesquiterpènes oxygénés, des monoterpènes oxygénés et des diterpènes oxygénés. L’extrait volatil de boutons de fleurs de Spartium junceum L. était principalement composé de composés aliphatiques. Par ailleurs, les résultats de l’évaluation des capacités anti-oxydantes des extraits (par les tests DPPH, ABTS, FRAP, ORAC et Folin-Ciocalteu) ont montrés que plusieurs plantes comme Cytisus scoparius L., Tussilago farfara L., Citrus aurantium L. ou Robinia pseudoacacia L. pourraient être des sources potentielles d’anti-oxydants naturels. D’un point de vue technologique, les comparaisons de l’utilisation de l’hydrodistillation (HD), de la distillation à la vapeur (SD) et de l’extraction par eau sub-critique (SWE) ont montrées que si la HD et la SD ont des effets limités sur la composition des huiles essentielles, la HD semble être une méthode plus efficace pour la récupération des composés anti-oxydants à partir des résidus de distillation que la SD tandis que la SWE s’avère être une technologie prometteuse pour l’extraction directe de ces molécules à partir des plantes. Si la composition minérale de l’eau lors de l’hydrodistillation n’a que des effets très limités sur les rendements d’extraction, les teneurs en ions calcium et bicarbonate des eaux ont par contre des effets décroissants significatifs sur la capacité anti-oxydante et sur la teneur phénolique totale des extraits aqueux et méthanoliques. Au vue de ces résultats, un concept amélioré de MAP-raffinerie a été développé en intégrant une extraction à l’eau sub-critique pour l’extraction des composés anti-oxydants des résidus d’extraction primaire. Selon ce nouveau concept, cinq extraits peuvent être obtenus à partir des matières végétales: un extrait volatil, un extrait aqueux, un extrait méthanolique, un extrait à l’eau sub-critique et in fine un résidu solide. Les premiers résultats ont montrés que la "MAP-raffinerie améliorée" augmente de manière significative la récupération des antioxydants par rapport à la MAP-raffinerie originale et permet d’envisager une valorisation plus facile du résidu solide en agro-matériaux du fait de sa faible teneur en eau résiduelle. / In both Midi-Pyrénées region (France) and Chongqing region (China), there are rich and underutilized medicinal and aromatic plants (MAP). Aiming at fully exploiting different molecules in these plants, the concept of MAP-refinery was developed and applied to several underutilized medicinal and aromatic plants in these two regions. Several water-based green extraction technologies of natural products (e.g. hydrodistillation, steam distillation and subcritical water extraction) were also investigated to look at their effects on essential oil composition and antioxidants recovery from selected plants. Firstly, lists of forgotten or underutilized medicinal and aromatic plants in both regions were established according to the rules of selection. From the lists, six plants in the Midi-Pyrénées region (Tussilago farfara L., Calendula arvensis L., Robinia pseudoacacia L., Geranium robertianum L., Cytisus scoparius L. and Spartium junceum L.) and three plants in the Chongqing region (Tussilago farfara L., Citrum aurantium L. and Saussurea costus) were finally selected for investigations. Then the MAP-refinery was applied to the selected plants in two regions in order to realise their global valorisation. Volatile extracts composition in the roots of Tussilago farfara L. and Calendula arvensis L., as well as flower buds of Spartium junceum L. were firstly investigated. The main chemical compounds in volatile extract from Tussilago farfara L. roots were sesquiterpene hydrocarbons and aliphatic compounds while main chemical compounds in volatile extract from Calendula arvensis L. roots were oxygenated sesquiterpenes, oxygenated monoterpenes and oxygenated diterpenes. The volatile extract from flower buds of Spartium junceum L. was mainly composed of aliphatic compounds. Antioxidant capacity evaluation results (by DPPH, ABTS, FRAC, ORAC and Folin-Ciocalteu tests) showed that several plant samples like Cytisus scoparius L., Tussilago farfara L., Citrum aurantium L. and Robinia pseudoacacia L. could be potential sources of natural antioxidants. Comparisons of hydrodistillation (HD), steam distillation (SD) and subcritical water extraction (SWE) showed that HD and SD had limited effects on essential oil composition but HD, SD and SWE had significant impacts on the recovery of antioxidants. Hydrodistillation seemed to be a better method for recovery of antioxidant compounds from residues of distillation than steam distillation. However, SWE appeared to be a more efficient method for direct extraction of antioxidant molecules (or phenolic compounds) from plants. In the hydrodistillation process, mineral contents in water were found to have very limited effects on yields of extracts but calcium and bicarbonate ions, had significant decreasing effects on antioxidant capacity and total phenolic content of both aqueous and methanolic extracts. Finally, an improved MAP-refinery was developed. Subcritical water was used for further extraction of antioxidant compounds from residues in original MAP-refinery. In this way, five parts could be obtained from plant materials: volatile extract, aqueous extract, methanolic extract, subcritical water extract and the final residue. The results showed that the improved MAP-refinery significantly increased the recovery of antioxidants compared with original MAP-refinery. This promising process will also allow a better valorisation of the final solid residue due to the lower content of residual water.