"Les dioxines" (PCDD/F : polychlorodibenzodioxines/furanes) sont des polluants organiques persistants émis dans l'atmosphère, provenant de combustions incomplètes. Cette étude concerne l'oxydation et la pyrolyse du dibenzofurane (DBF) choisie comme molécule modèle des PCDF. La réaction est étudiée dans un réacteur parfaitement agité entre 500 et 950°C, pour un temps de passage de 3 à 5s et à très faible concentration de DBF (~2 ppm) pour se rapprocher des conditions des incinérateurs (UIOM). Les espèces intermédiaires, formées lors de la décomposition du DBF, sont identifiées par GC/MS puis quantifiées par TD/GC/FID. Ces produits sont des dérivés du benzofurane, des composés aromatiques et poly-aromatiques. A partir de ces résultats, un mécanisme cinétique détaillé a pu être développé et validé. Ce mécanisme est ensuite utilisé pour simuler d'autres conditions opératoires et optimiser la zone de postcombustion des UIOM / "Dioxins" (PCDD/F) are persistent organic pollutants which are emitted in the atmosphere by several combustion and thermal processes. The present study concerns the oxidation and the pyrolysis of dibenzofuran which is chosen as a model molecule of polychrorodibenzofurans. The reaction is studied at very low concentration of dibenzofuran (~2 ppm) in a continuous perfectly stirred reactor between 3s and 5s, whereas temperature is ranging from 500°C to 950°C. During dibenzofuran decomposition, several intermediary species are formed; they are identified by GC/MS and then quantified by TD/GC/FID. The main products are derivatives of benzofuran, polyaromatic hydrocarbons and other volatile organic compounds. Taking into account our experimental results and the literature data, we have proposed and validated a detailed mechanism of DBF reaction. This mechanism is used to model the abatement of dioxins by total oxidation in the postcombustion area of a municipal waste incinerator

La valorisation de chaleur fatale industrielle en flux gazeux à haute température peut bénéficier de technologies de stockage thermique thermocline, fonctionnant sur la base d’un matériau de stockage céramique et d’un caloporteur gazeux (air). La diversité des gisements de chaleur fatale et des débouchés potentiels met en évidence la nécessité d’un procédé de stockage versatile et robuste. Ce travail de thèse consiste à accompagner le développement de l’entreprise Eco-Tech Ceram, dont les deux activités sont le développement d’une unité de stockage thermique, et le développement de matériaux céramiques issus de sous-produits industriels destinés à une utilisation dans de telles unités. Concernant l’axe stockage, il s’agit de réaliser une validation expérimentale du concept EcoStock via des essais sur des pilotes représentatifs, notamment concernant la sensibilité des performances au débit de décharge, et à la nature de la ressource thermique disponible en charge (débits et températures d’entrées variables).Concernant l’axe matériau, il s’agit de développer une céramique frittée issue de mâchefer d’incinérateur, et destinée à une utilisation en tant que matériau de garnissage dans un système thermocline à lit en vrac, via une approche expérimentale, dans une démarche d’écologie industrielle et avec l’objectif de diminuer autant que possible les coûts de production et les impacts environnementaux, en calquant les méthodes d’élaboration sur celles des céramiques de batiment (briques et tuiles) dont les capacités industrielles sont pré-existantes. r. / The recovery and valorization of high-temperature gaseous waste heat streams can benefit from the development of thermocline thermal energy storage, based on the use of a ceramic material as a solid filler and gases (including air) as heat transfer fluid. The wide diversity of waste heat streams implies developping a versatile and robust system, able to operate in such various conditions.This thesis aims at supporting the development of the company Eco-Tech Ceram, which focuses on developing a compact thermocline air/ceramic thermal storage unit (named EcoStock), and developing ceramics produced from industrial inorganic byproducts, designed to be used as thermal energy storage material. Regarding the « thermal storage » topic, this thesis is focused on the experimental validation of the EcoStock concept, through experimental campaigns on a representative pilot-scale system, especially regarding the influence of operating conditions over performances, and the sensitiviy of the system’s efficiency when discharged at different power level, or charged with low-quality heat streams (varying mass flow rate and inlet temperature during charging phase). Regarding the « ceramic » topic, this thesis is focused on developing a sintered ceramic based on municipal waste incinerator bottom ashes compatible with high temperature thermocline system, with an experimental approach, taking in consideration industrial potential of such ceramics by making industrial mass production of such material realistic, using already widely available industrial processes from the bricks and tiles industries.Keywords: thermal storage, thermocline, experimental validation, waste heat, high temperature, sintered ceramics, incinerator bottom ash valorization.

Os hidrocarbonetos policíclicos aromáticos (HPAs) são uma classe de substâncias químicas que podem ser geradas na combustão de matéria orgânica, e 17 destas substâncias são consideradas como poluentes prioritários pela Agência de Proteção Ambiental dos EUA (US EPA), em função de seu potencial tóxico e carcinogênico. Para identificar e quantificar os HPAs no ambiente de trabalho por cromatografia gasosa / espectrometria de massas, foram realizadas coletas de amostras ambientais em um incinerador de resíduos de serviços de saúde localizado na região da grande São Paulo e em três fundições de metais nas cidades de Loanda e Santa Isabel do Ivaí, no Estado do Paraná. A concentração de HPAs totais nas amostras ambientais coletadas no Incinerador foi de 0,36 - 1,72 µg/m3; na Fundição 1 de 0,72 - 4,56 µg/m3; na Fundição 2 de 2,32 - 6,52 µg/m3; na Fundição 3 de 0,19 - 3,72 µg/m3. Foi realizada também a coleta de amostras biológicas de trabalhadores expostos e não expostos, para a identificação e quantificação do indicador biológico de exposição o 1-hidroxipireno por cromatografia líquida com detector de fluorescência. A concentração de 1-hidroxipireno nas amostrados biológicas dos trabalhadores no Incinerador apresentou diferença estatisticamente siginificante entre o grupo exposto e o grupo controle; na Fundição 1 houve diferença estatisticamente pouco significante entre os grupos estudados; nas Fundições 2 e 3 não houve diferença estatisticamente significante entre os grupos estudados. / The Polycyclic Aromatics Hydrocarbons (PAH) are a class of chemicals that can to be generated by organic matter burning, and 17 of that chemicals are considered priority pollutant by Environmental Protection Agency (US EPA), because their toxicity and carcinogenicity potentials. To identify and to quantitify the PAH at workplace atmosphere by gas chromatography/mass spectrometry (GC/MS), it was conducted a environmental sampling in a waste incinerator, settled in the metropolitan São Paulo Region, and at three metals foundry settled in the Loanda City and Santa Isabel do Ivaí City, at Paraná State. The concentration of total PAH in the environmental samples collected in a waste incinerator was 0,36 - 1,72 µg/m3; at metals foundry 1 was 0,72 - 4,56 µg/m3; at metals foundry 2 was 2,32 - 6,52 µg/m3; at metals foundry 3 was 0,19 - 3,72 µg/m3. The biological samples of the workers was collected to identify and to quantitify the biological indicator urinary 1-hydroxypyrene (1-OH-Pyr) by high performance liquid chromatography/fluorescence detector (HPLC-Flu). The 1-OH-Pyr concentration in the biological samples of the exposed and control group in a waste incinerator presented a statistical significant difference; in the metals foundry 1 was observed a slight statistical significant difference; and in the metals foundry 2 and metals foundry 3 was not observed statistical significant difference.

Os hidrocarbonetos policíclicos aromáticos (HPAs) são uma classe de substâncias químicas que podem ser geradas na combustão de matéria orgânica, e 17 destas substâncias são consideradas como poluentes prioritários pela Agência de Proteção Ambiental dos EUA (US EPA), em função de seu potencial tóxico e carcinogênico. Para identificar e quantificar os HPAs no ambiente de trabalho por cromatografia gasosa / espectrometria de massas, foram realizadas coletas de amostras ambientais em um incinerador de resíduos de serviços de saúde localizado na região da grande São Paulo e em três fundições de metais nas cidades de Loanda e Santa Isabel do Ivaí, no Estado do Paraná. A concentração de HPAs totais nas amostras ambientais coletadas no Incinerador foi de 0,36 - 1,72 µg/m3; na Fundição 1 de 0,72 - 4,56 µg/m3; na Fundição 2 de 2,32 - 6,52 µg/m3; na Fundição 3 de 0,19 - 3,72 µg/m3. Foi realizada também a coleta de amostras biológicas de trabalhadores expostos e não expostos, para a identificação e quantificação do indicador biológico de exposição o 1-hidroxipireno por cromatografia líquida com detector de fluorescência. A concentração de 1-hidroxipireno nas amostrados biológicas dos trabalhadores no Incinerador apresentou diferença estatisticamente siginificante entre o grupo exposto e o grupo controle; na Fundição 1 houve diferença estatisticamente pouco significante entre os grupos estudados; nas Fundições 2 e 3 não houve diferença estatisticamente significante entre os grupos estudados. / The Polycyclic Aromatics Hydrocarbons (PAH) are a class of chemicals that can to be generated by organic matter burning, and 17 of that chemicals are considered priority pollutant by Environmental Protection Agency (US EPA), because their toxicity and carcinogenicity potentials. To identify and to quantitify the PAH at workplace atmosphere by gas chromatography/mass spectrometry (GC/MS), it was conducted a environmental sampling in a waste incinerator, settled in the metropolitan São Paulo Region, and at three metals foundry settled in the Loanda City and Santa Isabel do Ivaí City, at Paraná State. The concentration of total PAH in the environmental samples collected in a waste incinerator was 0,36 - 1,72 µg/m3; at metals foundry 1 was 0,72 - 4,56 µg/m3; at metals foundry 2 was 2,32 - 6,52 µg/m3; at metals foundry 3 was 0,19 - 3,72 µg/m3. The biological samples of the workers was collected to identify and to quantitify the biological indicator urinary 1-hydroxypyrene (1-OH-Pyr) by high performance liquid chromatography/fluorescence detector (HPLC-Flu). The 1-OH-Pyr concentration in the biological samples of the exposed and control group in a waste incinerator presented a statistical significant difference; in the metals foundry 1 was observed a slight statistical significant difference; and in the metals foundry 2 and metals foundry 3 was not observed statistical significant difference.

Deposits in municipal waste incinerators are very inhomogeneous in structure and constitution. They cause corrosion and reduce the efficiency, so they need to be removed frequently. Among other systems, operators use water cannons for the deposit removal. Two different removal mechanisms of water-cannon cleaning are suggested: A direct shattering of the deposit by the impact of the water jet, as well as the cracking caused by thermal stresses where droplets cool the deposits. As the contribution of each of the aforementioned mechanisms to the overall cleaning efficiency is unknown, we performed empirical investigations to determine the dominating effect. In a first experimental setup focusing on thermal stress, cold droplets were applied onto hot deposits taken from a waste incinerator. Results showed that the cleaning effect strongly depends on the deposit thickness and structure, so that the deposits could be categorised in three different groups. A second measurement campaign focused on the influence of deposit material, deposit temperature and water jet momentum. It could be shown that both deposit material and temperature have a significant effect on the cleaning efficiency, whereas an increase in water jet momentum only led to modest improvements. The combination of these two parameter studies implies that the influence of the thermal stress outweighs that of the momentum. This knowledge is applicable to the cleaning setup by increasing the temperature gradient.

根據環保署統計得知92年平均每人每日垃圾產生量為0.901公斤，該年垃圾總產量約為736萬公噸，清除處理廢棄物的方法，除了過去在各鄉鎮設置垃圾掩埋場，將廢棄物當地掩埋外，還有就是興建垃圾焚化廠來替代垃圾掩埋場，以減少取得垃圾掩埋場用地的困難。雖然傳統的公營、民營的一般掩埋場與衛生掩埋場則逐年減少，但仍高達了千座以上，全台各鄉鎮幾乎皆可看見。 因為垃圾處理設施的存在，令人覺得居家週遭的生活環境不寧適。廢棄物與其他環境介質之聯結有很大的相關性，單純針對廢棄物本身所造成的污染損害進行質損估算，是困難度較高的工作。但是垃圾處理設施本身所造成不寧適感受的損害並不包含在這些相關帳表中，而可以使用損害評估法的方式加以估算表示，因此本研究之目的在於調查垃圾處理設施帶給人們不寧適感受的質損。 此種不寧適的污染損害與賠償並不存在市場交易，無法藉由市場上的供給與需求來反應民眾所遭受的質損，因此本研究採用假設市場價值評估法(contingent valuation method)之問卷的方式，調查民眾願意改善環境品質的願付價值(willingness to pay)與願意接受環境惡化的情況下，願意接受的補償價值(willingness to accept)，民眾的WTP/WTA可視為受損害的環境價值，即為廢棄物處理設施所可能產生的質損。 / The producing amount of the one’s rubbish was 0.901 kilograms every day in 2003 according to the statistics in the Environmental Protection Administration. Total output of rubbish is about 7,360,000 metric tons that year. The method of cleaning the rubbish is building landfills and incinerators in every county. But now it is hard to get the specific land to build landfill, and the government policy is that an incinerator substitute for the all landfills in a county. Though the public and private landfills decrease gradually every year, it still had several thousand landfills in Taiwan. Because of the existence of the rubbish treatment facilities, it always makes the living environment of the surrounding area at home not feel peaceful and lose amenity. The purpose of this research lies in investigating the damage that the rubbish treatment facilities cause non-amenity to people. These kinds of pollution damage and compensation do not exist the market. We can’t use the supply, demand and price in the market to response the non-amenity damage of the feeling of Residents. So our research takes the survey to investigate how much resident would be willing to pay for improving the environment amenity and willing to accept for worsening the environment amenity. The people's WTP/WTA can be regarded as the value of the environmental damage from the rubbish treatment facilities.