Characterization of sulfur and chlorine behavior during pyrolysis of biomass and waste

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Transverse motion of cohesive powders in flighted rotary kilns: experimental study of unloading at ambient and high temperatures

International audienceThe transverse flow of cohesive powders in rotary kilns equipped with lifters was studied experimentally and theoretically. A laboratory device was built up in which the flow of uranyl difluoride (UO2F2), uranium sesquioxide (U3O8) and uranium dioxide (UO2) powders was filmed, recorded and analyzed using partly manual image analysis techniques. Experiments were performed both at room temperature and at high temperature. A constitutive law describing the powder discharge was derived, involving a relationship between the volume fraction of powder contained in a lifter and the angular position of this lifter. This law based on geometrical calculations is successfully compared with the experimental results of unloading

Étude expérimentale et modélisation de la réduction du minerai de fer par l'hydrogène

Cherchant des voies de réduction drastique des émissions de CO2 d origine sidérurgique (projet européen ULCOS), nous avons envisagé une réduction du minerai de fer par l hydrogène pur dans un réacteur du type four à cuve. L approche suivie a associé bibliographie, expérimentation et modélisation. Le déroulement de la réaction chimique et sa cinétique ont été analysés à partir d expériences thermogravimétriques et de caractérisations physico-chimiques d échantillons en cours de réduction. Un modèle cinétique spécifique a été mis au point, qui simule les réactions successives, les différentes étapes du transport de matière et le frittage éventuel du fer, à l échelle d une particule de solide. Enfin, un modèle numérique bidimensionnel du four à cuve a été écrit. Il décrit l évolution des températures et des compositions des solides et des gaz en tous points d un réacteur fonctionnant sous hydrogène. Une des originalités de ce modèle est l utilisation de la loi des temps caractéristiques additifs pour exprimer les vitesses des réactions. Celle-ci permet de coupler les deux échelles que sont celles des particules et du réacteur, tout en gardant des temps de calculs raisonnables. A partir des simulations réalisées, l influence des paramètres du procédé a été quantifiée. Des conditions opératoires optimales ont été dégagées, qui illustrent bien le potentiel du procédéIn an effort to find new ways to drastically reduce the CO2 emissions from the steel industry (ULCOS project), the reduction of iron ore by pure hydrogen in a shaft furnace was investigated. The work consisted of literature, experimental, and modelling studies. The chemical reaction and its kinetics were analysed on the basis of thermogravimetric experiments and physicochemical characterisations of partially reduced samples. A specific kinetic model was designed, which simulates the successive reactions, the different steps of mass transport, and possible iron sintering, at the particle scale. Finally, a 2-dimensional numerical model of a shaft furnace was developed. It depicts the variation of the solid and gas temperatures and compositions throughout the reactor. One original feature of the model is using the law of additive characteristic times for calculating the reaction rates. This allowed us to handle both the particle and the reactor scale, while keeping reasonable calculation time. From the simulation results, the influence of the process parameters was assessed. Optimal operating conditions were concluded, which reveal the efficiency of the hydrogen processNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF

Hydrogen Ironmaking: How It Works

A new route for making steel from iron ore based on the use of hydrogen to reduce iron oxides is presented, detailed and analyzed. The main advantage of this steelmaking route is the dramatic reduction (90% off) in CO2 emissions compared to those of the current standard blast-furnace route. The first process of the route is the production of hydrogen by water electrolysis using CO2-lean electricity. The challenge is to achieve massive production of H2 in acceptable economic conditions. The second process is the direct reduction of iron ore in a shaft furnace operated with hydrogen only. The third process is the melting of the carbon-free direct reduced iron in an electric arc furnace to produce steel. From mathematical modeling of the direct reduction furnace, we show that complete metallization can be achieved in a reactor smaller than the current shaft furnaces that use syngas made from natural gas. The reduction processes at the scale of the ore pellets are described and modeled using a specific structural kinetic pellet model. Finally, the differences between the reduction by hydrogen and by carbon monoxide are discussed, from the grain scale to the reactor scale. Regarding the kinetics, reduction with hydrogen is definitely faster. Several research and development and innovation projects have very recently been launched that should confirm the viability and performance of this breakthrough and environmentally friendly ironmaking process

New insights on the thermal decomposition of lanthanide(III) and actinide(III) oxalates: from neodymium and cerium to plutonium

International audienceLanthanides are often used as surrogates to study the properties of actinide compounds. Their behaviour is considered to be quite similar as they both possess f valence electrons and are close in size and chemical properties. This study examines the potential of using two lanthanides (neodymium and cerium) as surrogates for plutonium during the thermal decomposition of isomorphic oxalate compounds, in the trivalent oxidation state, into oxides. Thus, the thermal decomposition of neodymium, cerium and plutonium (III) oxalates are investigated by several coupled thermal analyses (TG-DTA/DSC-MS/FT-IR) and complementary characterisation techniques (XRD, UV-vis, FT-IR, SEM, carbon analyser) under both oxidizing and inert atmosphere. The thermal decomposition mechanisms determined in this study confirmed some previous results reported in the literature, among diverging propositions, while also elucidating some original mechanisms not previously considered. Calculated thermodynamic and kinetic parameters for the studied systems under both atmospheres are reported and compared with available literature data. Similarities and differences between the thermal behaviour of plutonium(III) and lanthanide(III) oxalates are outlined

Analyse environnementale de l'utilisation de biomasse pour la production de tuyaux en fonte

Les émissions élevées de CO2 de la filière industrielle de fabrication des tuyaux en fonte résultent pour l'essentiel de l'emploi massif de carbone fossile, charbon et coke, comme combustible et agent réducteur dans les procédés. Substituer du carbone issu de biomasse au carbone fossile en vue de réduire ces émissions de CO2, avec application au cas d'une usine lorraine, a été l'idée de départ de ce travail. Différents types de biomasse ont été envisagés. Le bois et la paille seraient localement disponibles en quantité suffisante pour autoriser une substitution partielle de 20 % du coke. Cette biomasse doit cependant être traitée thermiquement (séchage et pyrolyse) avant de satisfaire les spécifications techniques imposées par les procédés métallurgiques (agglomération, cokerie, haut fourneau). Six scénarios d'usage de la biomasse au haut fourneau ou à l'agglomération ont été sélectionnés. Pour les évaluer sur la base de leur mérite environnemental, nous avons réalisé une analyse de cycle de vie comparative en suivant une approche du type berceau à la porte. Point original de notre étude, l'inventaire de cycle de vie est issu de modèles systémiques des principaux procédés, spécifiquement développés et intégrés à un logiciel de diagrammes de flux. Grâce à ces modèles et notamment celui du haut fourneau, on a pu déterminer les taux de remplacement du coke par trois types de biomasse (charbon de bois en blocs, charbon de bois pulvérisé, bois torréfié pulvérisé) et prédire les modifications de fonctionnement qu'entrainerait l'injection de biomasse. Les résultats de l'analyse de cycle de vie montrent que l'injection de bois, carbonisé ou torréfié, sous forme pulvérisée aux tuyères du haut fourneau serait une solution intéressante d'un point de vue environnemental : baisse des émissions de gaz à effet de serre (-15 %) et des impacts sur la santé humaine et sur les écosystèmes. A l'heure actuelle cependant, le coût économique d'une telle solution demeure excessifHigh CO2 emissions from the industrial production of pig iron pipes are mainly due to the massive use of fossil carbon, coal and coke, as a fuel and/or a reducing agent in the processes. The use of biogenic carbon as a substitute for fossil carbon in order to reduce the CO2 emissions, in the case of an existing plant in Lorraine, was the starting point of our work. Different types of biomass were investigated. Local resources for wood and straw would be sufficient for a partial substitution for 20% of the coke. However, this kind of biomass should first undergo a thermal pretreatment step (drying and pyrolysis) to fit the technical requirements for the metallurgical processes (sinter plant, coke oven and blast furnace). Four scenarios of using biomass in the blast furnace or at the sinter plant were selected. To evaluate their environmental performances, we produced a comparative life cycle assessment, using a cradle-to-gate approach. An original feature of our study lies in the use of systems modeling for the determination of the life cycle inventories of the main processes, which were modeled using a flowsheeting software. From these models, particularly the model of the blast furnace, we could evaluate the replacement ratio of three biomass types (charcoal lumps, charcoal fines and torrefied wood fines) for the coke and predict the influence of biomass injection in the blast furnace on its operation. The results of the life cycle assessment show that the injection of pulverized, torrefied or carbonized, wood through the tuyeres of the blast furnace would be an attracting solution from an environmental point of view. It would reduce greenhouse gas emissions by 15%, as well as mitigate the impacts on human health and ecosystems. Yet, the costs associated to such a solution are currently too highMETZ-SCD (574632105) / SudocNANCY1-Bib. numérique (543959902) / SudocNANCY2-Bibliotheque electronique (543959901) / SudocNANCY-INPL-Bib. électronique (545479901) / SudocSudocFranceF