The chemical company Perstorp AB has a 50 MWth circulating fluidized bed to supply the production plant with process steam. The fuel mixture used shows a large variation with about 20 different fuel fractions that can be divided into the categories, residue wood chips, sludge, forest fuel, animal waste, industrial residues, and peat. From an economic and environmental perspective, the use of peat should be minimized because it is classified as a fossil fuel. Peat has positive combustion characteristics due to a combination of sulfur and silica based minerals that can reduce alkali chloride related corrosion. Therefore it is not always possible phase out peat without negatively affecting the boilers availability. Besides reducing CO2 emissions, it is desirable to reduce the use of additives such as limestone and to use cheap waste fractions as fuels when operating a boiler. Similar to peat, reduced use of limestone and the introduction of a new waste fractions can affect the boiler availability negatively. If less limestone is used the risk of agglomeration can increase and often waste products can contain ash elements problematic in both a agglomeration and corrosion perspective.The aim of this master thesis is to investigate the possibility of reducing the usage of peat by minimizing the limestone content and to see if it would be possible to add a new Na-rich waste fraction to the fuel mixture. This was investigated by determining first what fuels that are used and in what amounts. Each fuel was either sent for new elemental analysis or existing analyses were used depending on if it was deemed to be still representative. With the help of experienced personnel working with the boiler, future possible cases for fuel mixtures could be determined: Case 1. Replacing peat with forest fuels. Case 2. Replacing peat with residue wood chips. Case 3. Replacing both peat and animal waste with residue wood chips. Case 4. Introducing Na-rich fuel. The theoretical available SO2 content could be determined for each case and three limestone levels. For each case the CO2 emissions and the economic savings could be estimated when the peat were fully removed and the limestone content halved. From an SO2 perspective, the results indicate that it could be possible to phase out peat for cases 1-2 by adjusting the limestone levels but this would not be enough for case 3. Adding the Na-rich fuel could also be problematic and more investigation has to be put into potential additives and fuels to compensate for the additional Na.When peat is fully phased out in case 1-3 the CO2 emission would decrease by 10 000 tonCO2/year. Due to the cost of CO2 emissions, this could result in considerable monetary savings. From the results it is estimated that case 1 could save 9.1 million SEK/year, case 2 10.3 million SEK/year, and case 3 6.5 million SEK/year when the peat is fully removed. This does not include changes in availability and maintenance costs. / Kemiindustriföretaget Perstorp AB har en 50 MWth cirkulerande fluidiserad bädd panna för att förse produktionen med processånga. Bränsleblandningen som används visar en stor variation med ett 20-tal olika bränslefraktioner som kan delas in i kategorierna returflis (RT-flis), slam, skogsbränsle, slaktrester, industrirester och torv. Från ett ekonomiskt- och miljöperspektiv bör användningen av torv minimeras eftersom den är klassad som ett fossilt bränsle. Dock har torv positiva förbränningsegenskaper vilket beror på dess innehåll av såväl svavel som kiselbaserade mineraler vilka minskar korrosions förmågan för alkali-klorider. Därför är det inte alltid möjligt att fasa ut torven utan att riskera att försämra pannans tillgänglighet. Andra aspekter förutom minskade CO2 utsläpp som är fördelaktiga vid drift av en panna, är att minimera användningen av tillsatser som kalksten samt använda restprodukter som bränsle i största möjliga mån. Dock kan, som i fallet med torv, en minskad användning av kalksten och ett nytt restproduktbränsle ha potentiella negativa konsekvenser för pannans tillgänglighet. Om kalksten används i mindre utsträckning kan risken för klumpbildning i pannan, agglomerering, öka och ofta kan restprodukter från produktionen innehålla höga halter av problematiska grundämnen både i ett korrosions och agglomererings perspektiv.Syftet med detta examensarbete har varit att undersöka möjligheterna att minska användningen av torv och kalksten samt möjligheten att tillföra ett nytt Na-rikt bränsle till bränsleblandningen. Detta undersöktes genom att först bestämma vad som eldades och i vilka mängder. Genom att använda data från leveransrapporter (för bränslen och additiv) och bränsleanalyser. I de fall det fanns representativ bränsleanalys användes dessa, i övrigt provtogs och beställdes nya bränsleanalyser. Med hjälp av erfaren personal som jobbar med pannan kunde olika möjliga framtida bränsleblandningar bestämmas. Dessa bränsleblandningar delades in i olika scenarion eller case som det kallas här: Case 1. Ersätta torv med skogsbränsle. Case 2. Ersätta torv med RT-flis. Case 3. Ersätta både torv och biomal (slaktrester) med RT-flis. Case 4. Introduktion av Na-rikt restbränsle. Baserat på en tidigare kartläggning av askomvandlingen i pannan kunde det teoretiska tillgängliga SO2 halten i rökgaserna bestämmas för varje case för tre olika kalkstenshalter. För varje case kunde sedan CO2 utsläppen samt de ekonomiska besparingarna estimeras då torv var helt urfasad och kalkstensinnehållet halverat. Från ett SO2 perspektiv pekar resultaten på att det skulle vara möjligt att fasa ut torven helt genom att minska kalkstenen mellan 0-50 vikt% för case 1 och 2 men inte för case 3. Att tillsätta det Na-rika bränslet kan potentiellt vara problematiskt. För att elda detta Na-rika bränslet kan det krävas en ny additiv eller ett S-rikt bränsle för att balansera tillskottet av Na och därmed minska korrosionsrisken.Vid utfasning av samtlig torv minskar CO2 utsläppen i case 1-3 med runt 10 000 tonCO2/år. Eftersom utsläpp av fossil CO2 är beskattat, uppskattas de möjliga besparingarna som betydande, 9.1 miljoner SEK/år i case 1, 10.3 miljoner SEK/år case 2 och 6.5 miljoner SEK/år i case 3 inklusive inköps- och askhanteringskostnader.

A qualidade dos efluentes líquidos do Pólo Industrial de Belford Roxo e das águas do Rio Sarapuí foram avaliadas por meio de ensaios de toxicidade aguda com Daphnia similis, Ceríodaphnia dúbia e Danio rerio e ensaios de toxicidade crônica com Ceriodaphnia dúbia e Selenastrum capricornutum. Em associação ao monitoramento ecotoxicológico, foram realizados os procedimentos de Avaliação e Identificação da Toxicidade - AIT (Toxicity Identification Evaluation - TIE) os quais possibilitaram a identificação dos agentes tóxicos para as duas matrizes. Para o efluente, foi identificado o íon cloreto como principal agente tóxico, complementado por efeitos aditivos de metais, amônia e sulfeto. As águas do Rio Sarapuí apresentam os nutrientes fósforo e nitrogênio como principais agentes tóxicos, com toxicidade aditiva de metais, amônia e sulfeto. Embora a Estimativa de Impactos Ambientais a partir dos dados de toxicidade do efluente sugira impactos mínimos por parte do lançamento de efluentes do Pólo no compartimento água superficial, a qualidade das águas desse rio já apresenta por si só um impedimento à manutenção da vida aquática. O constante lançamento de esgoto não tratado compromete a qualidade das águas do rio Sarapuí, culminando num quadro de completa degradação devido ao aumento da concentração de nutrientes e matéria orgânica, que acaba por inviabilizar o correto equilíbrio desse ecossistema e suas interações ecológicas naturais. / The quality of Belford Roxo Industrial Plant effluent and water from Sarapuí River were evaluated with Daphnia similis, Ceriodaphnia dubia and Danio rerio acute and chronic toxicity tests. In association with the ecotoxicological monitoring, the Toxicity Identification Evaluation procedure were performed and the identification of the toxic compounds was possible. The Chloride ion was identified as the major toxic compound in the effluent with additional effects of Metals, Ammonium and Sulfide. For the Sarapuí River, the compounds of Phosphorus and Nitrogen were identified as the major toxic compounds with addictive effects of Metals, Ammonium and Sulfide. Although the environmental impact estimation based on the effluent toxicity suggests a minor impact on the water quality of Sarapuí River, this was already sufficiently contaminated to make impracticable the establishment of an aquatic community. The constant discharge of untreated sludge promotes the eutrophication of this water body and makes impossible the equilibrium of this ecosystem.

O presente estudo trata do problema da corrosão de armaduras em estruturas de concreto armado submetidas à penetração de cloretos. É amplamente reconhecido nos meios técnico e científico que, dentre os diversos processos causadores de patologias nas estruturas de concreto armado, destacam-se aqueles que desencadeiam a corrosão das armaduras. O processo de corrosão é iniciado quando a concentração de cloretos na interface armadura/concreto atinge um valor limite, despassivando a camada química protetora ao redor da armadura. A utilização de uma abordagem probabilística é capaz de tratar o problema de forma mais consistente, uma vez que as variáveis envolvidas no fenômeno possuem um alto grau de aleatoriedade associado. A formulação utilizada para a análise não linear mecânica emprega o método dos elementos finitos, utilizando o modelo de dano de Mazars para descrever o comportamento do concreto e o modelo elastoplástico para descrever o comportamento do aço. A lei de Fick é empregada para descrever o mecanismo de difusão dos íons cloretos no interior dos elementos de concreto armado e leis empíricas são utilizadas para representar a penalização das áreas de aço das armaduras bem como a redução de sua tensão de escoamento. A formulação utilizada para a análise probabilística emprega o FORM (First Order Reliability Method), o método de superfície de resposta e a simulação de Monte Carlo. Enfoque especial é dado na análise de estruturas hiperestáticas, com o objetivo de determinar a probabilidade de falha do sistema, sendo esta uma das contribuições desse estudo. Os resultados obtidos indicam de que forma os efeitos corrosivos considerados contribuem para a redução da durabilidade estrutural. / This work deals with the problem of reinforcement corrosion of concrete structures subjected to chloride penetration. It is widely recognized in the technical and scientific communities that, among the different processes which cause pathologies in reinforced concrete structures, reinforcement corrosion is one of the most relevant. The corrosion process starts when chloride concentration at the reinforcement/concrete interface reaches a threshold value, causing depassivation of the protecting chemical layer surrounding the armor. A probabilistic approach is capable of dealing with the problem in a more consistent manner, since the variables involved in the phenomenon have a high degree of randomness. The formulation used in the mechanical non-linear analysis utilizes the finite element method, employing Mazars\' damage model to describe the concrete behavior and the elastoplastic model to describe the steel behavior. Fick\'s law is used to describe the diffusion mechanism of chloride ions inside the concrete elements and empirical laws are used to represent the steel area reduction as well as the reduction of steel yield stress. The formulation used for the probabilistic analysis employs the FORM (First Order Reliability Method), the response surface method and the Monte Carlo simulation. A contribution of this study concerns the analysis of hyper-static structures, in order to evaluate the failure probability of the system, giving special attention to this type of problem. The obtained results show how the considered corrosive effects influences the structural durability reduction.

The aim of this study was to assess the strength, durability properties and corrosion resistance of concrete samples using supplementary cementitious blended materials. In this investigation, three supplementary concrete materials (SCMs) were used together with ordinary Portland Cement (OPC) to form cementitious blends at different proportions. The supplementary materials are silica fume (SF), ground granulated blast furnace slag (GGBS) and fly ash (FA). Sixteen (16) different proportions of the cementitious blends were produced. Tests carried out on concrete samples include slump test, compressive strength, oxygen permeability, sorptivity, porosity, chloride conductivity test, resistance to chloride and sulphate attack. The electrode potentials of tested samples were also observed using electrochemical measurements. Concrete specimens prepared with 10%, 20%, 30%, 40%, up to 60% of blended cements replacement levels were evaluated for their compressive strength at, 7, 14, 28, 90 and 120 days while the specimens were evaluated for durability tests at 28, and 90 days respectively. The results were compared with ordinary Portland cement concrete without blended cement. Voltage, and temperature measurements were also carried out to understand the quality of concrete. The corrosion performance of steel in reinforced concrete was studied and evaluated by electrochemical half-cell potential technique in both sodium chloride, and magnesium sulphate solutions respectively. The reinforced concrete specimens with centrally embedded 12mm steel bar were exposed to chloride and sulphate solutions with the 0.5 M NaCl and MgSO4 concentrations respectively. An impressed voltage technique was carried out to evaluate the corrosion resistance of the combination of quaternary cementitious blended cement, so as to get the combination with optimum performance. Improvement of strength, durability, and corrosion resistance properties of blended concrete samples are observed at different optimum percentages for binary, ternary and quaternary samples. The effect of cementitious blends is recognized in limiting the corrosion potential of the tested SCM concrete samples. Generally, the cementitious blends with limited quantity of SF to 10% have the potential to produce satisfactory concrete. These should however be used for low cost construction, where high quality concrete is not required. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

<p>This thesis concerns the study of reaction mechanisms by means of kinetic isotope effects (KIEs). Studies of the nucleophilic bimolecular substitution (S_N2) reaction had the dual purpose of improving our fundamental understanding of molecular reactivity and assessing the ability of kinetic isotope effects to serve as mechanistic tools. The transition state of the S_N2 reaction between a cyanide ion and ethyl chloride in tetrahydrofuran was found to be reactant like and only slightly tighter than has been found previously for the same reaction in dimethyl sulphoxide. One conclusion was that the transition-state structure in this reaction was predicted fairly well by the theoretical calculations, even without solvent modelling. The S_N2 reactions between cyanide ions and <i>para</i>-substituted benzyl chlorides were found to have reactant-like transition states, of which the C_α-Cl bond was most influenced by the <i>para</i>-substitution. Theoretical calculations indicated that the chlorine KIEs could be used as probes of the substituent effect on the C_α-Cl bond if bond fission was not too advanced in the transition state. Furthermore, the nucleophile carbon ¹¹C/¹⁴C KIEs were determined for the reactions between cyanide ions and various ethyl substrates in dimethyl sulphoxide.</p><p>Precision conductometry was employed to estimate the aggregation status of tetrabutylammonium cyanide in tetrahydrofuran and in dimethyl sulphoxide, which is of interest as tetrabutylammonium cyanide is frequently used as the nucleophilic reagent in mechanistic investigations and synthetic reactions. The tendency for ion-pair formation was found to be very slight, significant, and very strong in dimethyl sulphoxide, water, and tetrahydrofuran, respectively. </p><p>The nitrogen kinetic isotope effect on monoamine oxidase B catalysed deamination of benzylamine was determined in an attempt to obtain conclusive evidence regarding the mechanism of the oxidation. Monoamine oxidase is an important drug target in connection with the treatment of, for example, depression and Parkinson’s disease, and knowledge on how the enzyme effects catalysis would facilitate the design of highly selective and efficient inhibitors.</p>

This thesis concerns the study of reaction mechanisms by means of kinetic isotope effects (KIEs). Studies of the nucleophilic bimolecular substitution (SN2) reaction had the dual purpose of improving our fundamental understanding of molecular reactivity and assessing the ability of kinetic isotope effects to serve as mechanistic tools. The transition state of the SN2 reaction between a cyanide ion and ethyl chloride in tetrahydrofuran was found to be reactant like and only slightly tighter than has been found previously for the same reaction in dimethyl sulphoxide. One conclusion was that the transition-state structure in this reaction was predicted fairly well by the theoretical calculations, even without solvent modelling. The SN2 reactions between cyanide ions and para-substituted benzyl chlorides were found to have reactant-like transition states, of which the Cα-Cl bond was most influenced by the para-substitution. Theoretical calculations indicated that the chlorine KIEs could be used as probes of the substituent effect on the Cα-Cl bond if bond fission was not too advanced in the transition state. Furthermore, the nucleophile carbon 11C/14C KIEs were determined for the reactions between cyanide ions and various ethyl substrates in dimethyl sulphoxide. Precision conductometry was employed to estimate the aggregation status of tetrabutylammonium cyanide in tetrahydrofuran and in dimethyl sulphoxide, which is of interest as tetrabutylammonium cyanide is frequently used as the nucleophilic reagent in mechanistic investigations and synthetic reactions. The tendency for ion-pair formation was found to be very slight, significant, and very strong in dimethyl sulphoxide, water, and tetrahydrofuran, respectively. The nitrogen kinetic isotope effect on monoamine oxidase B catalysed deamination of benzylamine was determined in an attempt to obtain conclusive evidence regarding the mechanism of the oxidation. Monoamine oxidase is an important drug target in connection with the treatment of, for example, depression and Parkinson’s disease, and knowledge on how the enzyme effects catalysis would facilitate the design of highly selective and efficient inhibitors.

Lodging poses a serious limitation to successful economic production of small grain cereals and can lead to extensive yield and quality losses. Plant growth regulators (PGR's) that reduce plant height and lodging have been employed in management systems in Europe and the United States, however, these compounds have not been evaluated on commercial cultivars of wheat, barley and oats in South Africa. Current recommendations to reduce lodging include limiting N inputs, seeding rates and critical irrigations, all of which may also limit yield potential and grain quality. The objectives of this study were to assess the effects of two common stem-elongation-inhibiting PGR's (chlormequat chloride and ethephon) on the growth, development, and agronomic characteristics of wheat, barley and oats. The aim of the study was to introduce an additional component of intensive cereal management in the form of PGR's, and to allow producers to implement intensive production practices without incurring losses due to lodging. Field trials were conducted with each of the three cereal crops in the 2003 and 2004 seasons at Vaalharts and Bethlehem. The PGR's were applied separately and in combination with each other to lodging-tolerant and -susceptible cultivars (wheat and oats) at different stages of development (tillering, elongation, flag leaf stage). The PGR's were also tested in combination with different levels of N (barley) applied at the haulm elongation stage, the flag leaf stage, or both. The PGR chlormequat produced negligible effects on plant height, lodging, yield, or quality components in all of the tested cultivars . Ethephon and the PGR combination successfully reduced plant height (by 120 to 150mm) and lodging (by 25 to 94%) when applied to the lodging susceptible cultivars of wheat and oats at the flag leaf stage or as a split application to the barley cultivar "Puma" (plant height and lodging reduced by 180 to 230mm and 83 to 92% respectively). Effects on grain yield were variable, ranging from occasional reductions (by 3 t ha(-1) and improvements (by 1 t ha(-1) with the barley, and no effects with the wheat and oats. Wheat quality parameters such as protein content and hectolitre mass were improved by 2 and 4% respectively. However, the nature of the responses was highly dependent on the times of application with later applications producing the greatest positive effects on quality, yield and lodging reductions. Additionally, ethephon and the PGR combination allowed higher levels of N to be employed without increases in lodging of barley. Generally, ethephon and the PGR combination applied at the flag leaf stage of growth are suitable anti-lodging tools for small grain cereal production and should be employed as an insurance measure against lodging in intensive management systems. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2006.

La corrosion des échangeurs de chaleur est un problème économique et technique majeur des Unités de Valorisation Energétique de Ordures Ménagères (UVEOM). Elle est causée par l’action combinée (i) des gaz de combustion contenant notamment HCl et SO2 et (ii) des cendres riches en chlorures et sulfates alcalins, et sels de métaux lourds. Les travaux présentés dans ce mémoire s’inscrivent dans le projet ANR SCAPAC (n°11-RMNP-0016) et portent sur l’influence des paramètres expérimentaux (température, teneur en chlorures dans les cendres, présence de gaz corrosifs et présence de chlorures de métaux lourds dans les cendres) sur la tenue à la corrosion de deux alliages utilisés en milieu UVEOM : l’acier 16Mo3 et l’alliage base nickel Inconel 625. Ces travaux ont permis de mettre en évidence que la présence de phases fondues, l’augmentation de la teneur en chlorures, la présence de 10% en masse de ZnCl2 dans les mélanges de cendres et la présence de gaz corrosifs (HCl, SO2) dans l’atmosphère sont trois facteurs qui ont induit une corrosion plus importante sur les matériaux, de manière plus prononcée sur l’alliage base fer. Une autre partie du travail s’est focalisée sur l’influence des éléments d’alliage Fe, Cr et Mo. Des alliages « modèles » dont les compositions oscillent autour de la composition de l’alliage Inconel 625 commercial ont été synthétisés par fusion haute fréquence et leur tenue à la corrosion a été évaluée sous air et sous atmosphère corrosive. La bonne optimisation de l’alliage commercial a ainsi été démontrée sous air. Sous atmosphère gaz corrosifs, une teneur en chrome supérieure à 22% massique s’est montrée indispensable à la bonne tenue de l’alliage / Corrosion of heat exchangers is an economic and technical issue in Waste-to-energy plants. It is caused by the combined action of (i) flue gas containing HCl and SO2 and (ii) chlorides and alkali sulfates rich ash. This work is part of the ANR project SCAPAC (supported by the ANR-11-RMNP 0016) and focused on the influence of experimental parameters on the corrosion behavior of two commercial alloys used in Waste-to-Energy plants: the 16Mo3 steel and the nickel-based alloy Inconel 625. This study allowed to highlight that the presence of molten phase, the increase in the chloride content, the presence of 10% by weight of ZnCl2 in the ash mixtures and the presence of corrosive gases (HCl, SO2) in the atmosphere are three factors that have induced an higher corrosion of materials, more pronounced on the iron alloy base. Another part of the work has been focused on the influence of alloying elements Fe, Cr and Mo. Thus, model alloys with compositions oscillating around the composition of Inconel 625 commercial alloy were synthesized by high frequency induction and their corrosion resistance was evaluated in air and in corrosive atmosphere. Good optimization of the commercial alloy has been demonstrated in air. In corrosive atmosphere, a minimum chromium content was required to obtain a good corrosion resistance

Made available in DSpace on 2014-10-09T12:52:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:49Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:52:19Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:00:49Z (GMT). No. of bitstreams: 0 / A qualidade dos efluentes líquidos do Pólo Industrial de Belford Roxo e das águas do Rio Sarapuí foram avaliadas por meio de ensaios de toxicidade aguda com Daphnia similis, Ceríodaphnia dúbia e Danio rerio e ensaios de toxicidade crônica com Ceriodaphnia dúbia e Selenastrum capricornutum. Em associação ao monitoramento ecotoxicológico, foram realizados os procedimentos de Avaliação e Identificação da Toxicidade - AIT (Toxicity Identification Evaluation - TIE) os quais possibilitaram a identificação dos agentes tóxicos para as duas matrizes. Para o efluente, foi identificado o íon cloreto como principal agente tóxico, complementado por efeitos aditivos de metais, amônia e sulfeto. As águas do Rio Sarapuí apresentam os nutrientes fósforo e nitrogênio como principais agentes tóxicos, com toxicidade aditiva de metais, amônia e sulfeto. Embora a Estimativa de Impactos Ambientais a partir dos dados de toxicidade do efluente sugira impactos mínimos por parte do lançamento de efluentes do Pólo no compartimento água superficial, a qualidade das águas desse rio já apresenta por si só um impedimento à manutenção da vida aquática. O constante lançamento de esgoto não tratado compromete a qualidade das águas do rio Sarapuí, culminando num quadro de completa degradação devido ao aumento da concentração de nutrientes e matéria orgânica, que acaba por inviabilizar o correto equilíbrio desse ecossistema e suas interações ecológicas naturais. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP