Дисертації з теми "Nickel Vanadium"

Les pétroles utilisés en raffinage étant de plus en plus lourds et chargés en métaux et hétéroélements, il est d’une grande importance pour les activités de raffinage de connaître la spéciation de ces espèces au sein des produits pétroliers et leurs comportements durant les procédés de raffinage. Afin d’apporter des réponses à cette problématique des techniques de caractérisation élémentaire et moléculaire ont été utilisées notamment par ICP MS Haute Résolution et FT ICR MS respectivement. Ces techniques analytiques sont appliquées à différents échantillons pétroliers provenant parfois de procédés de raffinage et les informations obtenues au niveau élémentaire et moléculaire sont utilisées de manières complémentaires pour améliorer notre compréhension des mécanismes se produisant au sein de nos échantillons durant les activités de raffinage
The crude oils available for the refining industry are heavier and heavier and more concentrated in metals and heteroelements. It is thus of great importance to study the speciation of these species within the petroleum products and their behavior during the refining processes. To answer that problematic, elemental and molecular characterization techniques have been used, mainly High Resolution ICP MS and FT ICR MS for the elemental and molecular characterization respectively. The analytical techniques quoted are used for the analysis of several petroleum products sometimes originating from refining processes and the information obtained at the elemental and molecular level are combined to improve our understanding of the mechanisms occurring within our samples during refining activities

L'objectif de ce travail est de preciser l'influence de divers parametres: temps, temperature, pression d'eau, ajout de vanadium ou de nickel sur les proprietes de zeolithe y et de catalyseurs de craquage. Ces solides sont caracterises par diverses methodes physiques et physicochimiques: microscopie electronique a transmission, spectroscopie de photoelectron x (xps), adsorption de pyridine et a l'aide d'une reaction modele: la transformation du methylcyclohexane. La premiere partie concerne la desalumination de zeolithes nh#4y en fonction des conditions du traitement hydrothermal. Le temps, la temperature et la pression d'eau ont un effet positif sur la desalumination de la charpente, les especes aluminiques extrareseau se localisant preferentiellement a la surface des cristallites. La seconde partie montre l'effet du nickel et du vanadium. Le vanadium diminue la stabilite des zeolithes ce qui se traduit par une baisse de l'activite catalytique. Cette baisse d'activite ne provient pas seulement de la destabilisation des zeolithes mais aussi de l'echange de sites protoniques par des especes vanadium cationiques. Le nickel agit principalement sur la selectivite. Le traitement hydrothermal a 750c provoque une migration des especes vanadium. Cette migration tres importante dans le cas de la zeolithe ushy est beaucoup plus limitee dans le cas de la zeolithe lay et du catalyseur de craquage par suite de reactions entre le vanadium et le lanthane ou des constituants de la matrice

Abstract Water-related problems are increasing globally, and new, low-cost technologies are needed to resolve them. Lignocellulosic waste materials contain reactive functional groups that can be used to provide a bio-based platform for the production of water treatment chemicals. Research on bio-based ion exchange materials in the treatment of real wastewaters is needed. In this thesis, anion exchange materials were prepared through chemical modification (epichlorohydrin, ethylenediamine and triethylamine) using five Finnish lignocellulosic materials as bio-based platforms. Scots pine sawdust and bark (Pinus sylvestris), Norway spruce bark (Picea abies), birch bark (Betula pendula/pubescens) and peat were chosen due to their local availability and abundance. The focus was placed on NO3- removal, but uptake of heavy metals, such as nickel, was also observed and studied. Studies on maximum sorption capacity, mechanism, kinetics, and the effects of temperature, pH and co-existing anions were used to elucidate the sorption behaviour of the prepared materials in batch and column tests. All five materials removed over 70% of NO3- at pH 3–10 (initial conc. 30 mg N/l). Quaternized pine sawdust worked best (max. capacity 32.8 mg NO3-N/g), and also in a wide temperature range (5–70°C). Column studies on quaternized pine sawdust using mining wastewater and industrial wastewater from a chemical plant provided information about the regeneration of exhausted material and its suitability for industrial applications. Uptake of Ni, V, Co and U was observed. Column studies proved the easy regeneration and reusability of the material. For comparison, pine sawdust was also modified using N-(3-chloro-2-hydroxypropyl) trimethylammonium chloride and utilized to remove NO3- from groundwater and industrial wastewater. A maximum sorption capacity of 15.3 mg NO3-N/g was achieved for the synthetic solution. Overall, this thesis provides valuable information about bio-based anion exchange materials and their use in real waters and industrial applications
Tiivistelmä Edullisia ja kestäviä vedenkäsittelytekniikoita tarvitaan kasvavien vesiongelmien ratkaisemiseen. Lignoselluloosaa, kuten sahanpurua, syntyy suuria määriä teollisuuden sivutuotteena. Sen reaktiivisia funktionaalisia ryhmiä voidaan modifioida kemiallisesti ja valmistaa siten biopohjaisia vedenkäsittelykemikaaleja. Tutkimustietoa oikeiden jätevesien puhdistuksesta biopohjaisilla ioninvaihtomateriaaleilla tarvitaan lisää, jotta materiaalien käyttöä voidaan kehittää ja edistää. Tässä väitöstyössä valmistettiin anioninvaihtomateriaaleja modifioimalla kemiallisesti viittä suomalaista lignoselluloosamateriaalia: männyn sahanpurua ja kuorta (Pinus sylvestris), kuusen kuorta (Picea abies), koivun kuorta (Betula pendula/pubescens) ja turvetta. Menetelmässä käytettiin epikloorihydriiniä, etyleenidiamiinia ja trietyyliamiinia orgaanisessa liuotinfaasissa. Työssä keskityttiin erityisesti nitraatin poistoon sekä synteettisistä että oikeista jätevesistä. Materiaalien soveltuvuutta teollisiin sovelluksiin arvioitiin maksimisorptiokapasiteetin, sorptioisotermien, kinetiikka- ja kolonnikokeiden sekä pH:n, lämpötilan ja muiden anionien vaikutusta tutkivien kokeiden avulla. Kaikki viisi kationisoitua tuotetta poistivat yli 70 % nitraatista laajalla pH-alueella (3–10). Kationisoitu männyn sahanpuru osoittautui parhaaksi materiaaliksi (32,8 mg NO3-N/g), ja se toimi laajalla lämpötila-alueella (5–70°C). Kolonnikokeet osoittivat sen olevan helposti regeneroitavissa ja uudelleenkäytettävissä. Tuotetta testattiin myös kaivos- ja kemiantehtaan jäteveden käsittelyyn, ja kokeissa havaittiin hyviä nikkeli-, uraani-, vanadiini- ja kobolttireduktioita. Männyn sahanpurua modifioitiin vertailun vuoksi myös kationisella monomeerilla, N-(3-kloro-2-hydroksipropyyli)trimetyyliammoniumkloridilla. Tuotteen maksimisorptiokapasiteetiksi saatiin 15,3 mg NO3-N/g ja se poisti nitraattia saastuneesta pohjavedestä. Kokonaisuudessaan väitöskirjatyö tarjoaa uutta tietoa biopohjaisten ioninvaihtomateriaalien valmistamisesta ja niiden soveltuvuudesta oikeiden teollisuusjätevesien käsittelyyn

[ES] La presente tesis doctoral se sitúa en el marco de la actual transición energética, que plantea la sustitución progresiva de materias primas de origen fósil por fuentes renovables, tanto para la obtención de productos químicos como para la producción de combustibles. En este contexto de transición paulatina a las renovables, y teniendo en cuenta los últimos pronósticos, las fuentes fósiles (fundamentalmente gas natural) y derivados de la biomasa, jugarán un papel fundamental durante el cambio. Se ha llevado a cabo un estudio sobre el empleo de óxidos metálicos (basados en bronces de wolframio o en óxido de níquel), como catalizadores para: i) la transformación de derivados de biomasa: de glicerol a acroleína/ácido acrílico; y de compuestos oxigenados de cadena corta presentes en efluentes acuosos (procedentes de tratamientos de extracción de bio-aceites de pirolisis) a combustibles; y ii) la transformación de componentes del gas natural, concretamente la obtención de etileno a partir de etano, mediante deshidrogenación oxidativa (ODH). El trabajo se presenta desde una perspectiva de la química de materiales, haciendo hincapié en las propiedades fisicoquímicas de los distintos sistemas catalíticos, empleando técnicas de caracterización convencionales e in situ, además de reacciones modelo (transformación de metanol y etanol), con el objetivo de entender las funciones catalíticas presentes en cada caso. Tanto para la transformación de glicerol en fase gas, como para la valorización de mezclas acuosas de compuestos oxigenados de cadena corta, se han utilizado catalizadores basados en bronces de wolframio. Se ha tratado de poner de manifiesto la gran versatilidad composicional y estructural (con el consiguiente control de las propiedades funcionales), que presentan este tipo de materiales. En este sentido, las propiedades ácidas y redox de catalizadores W-V-O pueden ser moduladas, para una misma concentración de vanadio, mediante el control de la relación de fases cristalinas (hexagonal y monoclínica) del óxido de wolframio. Este efecto se ha estudiado empleando la transformación aeróbica de metanol como reacción "test", y tiene una gran influencia en la deshidratación oxidativa de glicerol a ácido acrílico. A su vez, mediante la sustitución isomórfica de wolframio por niobio (en el sistema WO3-Nb2O5) es posible controlar la relación de centros ácidos de tipo Brönsted y Lewis en la superficie de los materiales. Por un lado, los catalizadores con una alta relación Brönsted/Lewis se han mostrado más efectivos en la deshidratación de glicerol a acroleína, mientras que los catalizadores con altas concentraciones de centros de tipo Lewis presentan altos rendimientos a productos de condensación de compuestos oxigenados de cadena corta. Adicionalmente se han estudiado las diferencias entre catalizadores (bien óxidos mixtos W-V-O o W-Nb-O) preparados mediante un método hidrotermal o mediante reflujo, así como el efecto de la utilización de un soporte mesoporoso (KIT-6), sobre sus propiedades catalíticas en la transformación aeróbica en fase gaseosa de etanol y glicerol. Finalmente, en lo que concierne a la transformación de componentes del gas natural, se han empleado materiales basados en óxido de níquel (soportado sobre distintos óxidos y/o promovido con distintos metales) como catalizadores para la ODH de etano. En este caso el estudio se ha centrado fundamentalmente en dilucidar los efectos de promotores y soportes en la naturaleza y propiedades fisicoquímicas del óxido de níquel, los cuales dan lugar a un cambio drástico en sus propiedades catalíticas. Así, se ha observado que modificando la reducibilidad y las características superficiales del óxido de níquel es posible transformar un catalizador muy poco selectivo en la ODH de etano (como es el NiO, con una selectividad a etileno del 30 %) en uno de los catalizadores más selectivos para llevar a cab
[CAT] Aquesta tesi doctoral es situa dins del marc de l'actual transició energètica, la qual planteja la substitució progressiva de les primeres matèries d'origen fòssil per fonts renovables, tant per a l'obtenció de productes químics com per a la producció de combustibles. En aquest context de transició gradual a les renovables, i tenint en compte els últims pronòstics, les fonts fòssils (principalment el gas natural) i els derivats de la biomassa, exerciran un paper fonamental durant aquest canvi. S'ha dut a terme un estudi sobre la utilització d'òxids metàl·lics (basats en bronzes de wolframi o en òxid de níquel), com a catalitzadors per a: i) la transformació de derivats de la biomassa: de glicerol a acroleïna/àcid acrílic; i de compostos oxigenats de cadena curta presents en efluents aquosos (procedents de tractaments d'extracció de bio-olis de la piròlisi) a combustibles; i ii) la transformació de components del gas natural, concretament l'obtenció d'etilè a partir d'età, mitjançant la deshidrogenació oxidativa. El treball es presenta des del punt de vista de la química de materials, posant l'accent en les propietats fisicoquímiques dels diferents sistemes catalítics, utilitzant tècniques de caracterització convencionals i in situ, a més de reaccions model, amb l'objectiu d'entendre les funcions catalítiques presents en cadascun dels casos. Tant per a la transformació del glicerol en fase gasosa com per a la valorització de les mescles aquoses de compostos oxigenats de cadena curta, s'han utilitzat catalitzadors basats en bronze de wolframi. S'ha intentat posar de manifest la gran versatilitat de composicions i estructures (amb el conseqüent control de les propietats funcionals) que presenten aquest tipus de materials. En aquest sentit, les propietats àcides i redox dels catalitzadors de W - V - O poden ser modulades, per a una mateixa concentració de vanadi, mitjançant el control de la relació de fases cristal·lines (hexagonal i monoclínica) de l'òxid de wolframi. Aquest efecte s'ha estudiat utilitzant la transformació aeròbica de metanol com a reacció "test", i presenta una gran influència en la deshidratació oxidativa de glicerol a àcid acrílic. Al mateix temps, mitjançant la substitució isomòrfica de wolframi per niobi (en el sistema WO3 - Nb2O5), és possible controlar la relació de centres àcids de tipus Brönsted i Lewis en la superfície dels materials. Per una part, els catalitzadors que presenten una relació Brönsted / Lewis alta s'han mostrat més efectius en la deshidratació de glicerol a acroleïna, mentre que els catalitzadors amb unes altes concentracions de tipus Lewis presenten alts rendiments a productes de condensació de compostos oxigenats de cadena curta. Addicionalment, s'han estudiat les diferències entre catalitzadors (ja siguin òxids mixtos W-V-O o W-Nb-O) preparats mitjançant un mètode hidrotermal o mitjançant un mètode de reflux, així com l'efecte que presenta la utilització d'un suport mesoporós (KIT-6), sobre les seves propietats catalítiques en la reacció de transformació aeròbica en fase gasosa d'etanol i glicerol. Finalment, pel que fa referència a la transformació de components del gas natural, s'han utilitzat materials basats en òxid de níquel (suportat sobre diferents òxids i/o promoguts amb diferents metalls) i catalitzadors per a la deshidrogenació oxidativa d'età. En aquest cas, l'estudi s'ha focalitzat principalment en dilucidar els efectes de promotors i suports en la naturalesa i propietats fisicoquímiques de l'òxid de níquel, els quals impliquen un canvi dràstic en les seves propietats catalítiques. Així doncs, s'ha observat que modificant la reductibilitat i les característiques superficials de l'òxid de níquel és possible transformar un catalitzador molt poc selectiu en la deshidrogenació oxidativa de l'età (com és el cas del NiO, amb una selectivitat a l'etilè del 30%) en un dels cata
[EN] The present doctoral thesis is set within the scope of the current energy transition, which considers the progressive substitution of non-renewable fossil sources by renewable feedstocks for the production of chemicals and fuels. In this context of gradual transition, and according to recent energy outlooks, fossil sources (especially natural gas) and biomass feedstocks will play a key role during the shift. A study on the use of metal oxides (based on tungsten bronzes or nickel oxides) as catalysts for different reactions has been conducted. Particularly, they have been studied as catalytic materials for: i) the transformation of biomass-derived feedstocks: glycerol transformation into acrolein/acrylic acid, and the transformation of short-chain oxygenates present in aqueous effluents (derived from extraction processes of pyrolysis bio-oils) into fuels; and ii) the valorization of natural gas components, i.e. the transformation of ethane into ethylene by oxidative dehydrogenation. The work is presented from a materials chemistry perspective, emphasizing the physicochemical characteristics of the different catalytic systems by using conventional and in situ characterization techniques and model reactions (gas phase methanol and ethanol transformation); with the aim of understanding the specific catalytic functionalities present in each case. For both gas phase glycerol transformation and the valorization of short-chain oxygenates aqueous mixtures, catalyst based on tungsten oxide bronzes have been used. The compositional and structural versatility of this structural types (with the subsequent control of their functional properties) will be highlighted. In this sense, the acid-redox properties of W-V-O catalysts can be modulated by controlling the crystalline phase composition in the materials (i.e. hexagonal and monoclinic polymorphs of tungsten oxide) at a fixed V concentration. This effect has been studied by using the gas-phase aerobic transformation of methanol as a surface test reaction. The concentration of the hexagonal and monoclinic polymorphs in the catalysts has also an important influence in the gas-phase transformation of glycerol into acrylic acid. Also, it is possible to control the Brönsted/Lewis acid nature of the surface by the isomorphic substitution of Nb for W in WO3-Nb2O5 system. On the one hand, catalysts showing a higher proportion of Brönsted acid sites are more effective in the glycerol dehydration to acrolein. On the other hand, materials with a higher concentration of Lewis acid sites display high yields to condensation products in the aqueous phase valorization of short chain oxygenates. Additionally, the differences between W-V-O and W-Nb-O catalysts prepared by both reflux and hydrothermal methods have been studied. Also the effect of adding a mesoporous KIT-6 silica as support on the catalytic performance in the gas phase transformation of ethanol and glycerol will be underlined. Considering the transformation of natural gas components, nickel oxide-based materials were chosen (either supported on different oxides and/or promoted with different metals) to perform the oxidative dehydrogenation (ODH) of ethane. In this case the study has been focused on elucidating the effects of both promoters and supports on the nature and physicochemical features of nickel oxide, which lead to a drastic change in the catalytic behavior of these materials. This way, it has been observed that by the modification of the reducibility and the chemical nature of nickel oxide, it is possible to transform an apparently non-selective catalyst in the ODH of ethane (like NiO, showing a selectivity to ethylene of ca. 30 %) into one of the most selective catalysts reported in the literature (presenting a selectivity to ethylene of ca. 90 %).
También me gustaría agradecerle al Prof. Avelino Corma, investigador principal del proyecto SEV-2012-0267, a través del cual he podido realizar mi tesis doctoral enel Instituto de Tecnología Química (SVP-2014-068669).
Delgado Muñoz, D. (2019). Catalytic valorization of natural gas and biomass-derived feedstocks by metal oxides [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/122298
TESIS

La presence de vanadium et de nickel dans les bruts lourds pose des problemes au niveau de leur raffinage et de l'utilisation de coupes lourdes. Ces metaux sont presents dans le bruts et dans les residus lourds sous la forme de composes organometalliques: les metalloporphyrines. Cette etude a eu pour but de rechercher un procede utilisant des microorganises permettant la demetallisation biologique en presence d'eau d'un residu petrolier solide lourd: un asphalte n-c5 provenant d'un brut boscan. Des inoculums microbiens mixtes capables d'utiliser les metalloporphyrines en tant que sources d'azote et de solubiliser les metaux ont ete recherches. Les consortiums bacteriens utilises sont issus d'hydrocarbures et de sols ayant recu des hydrocarbures. Au moyen d'un dispositif de percolation de colonnes d'asphalte, une activite biologique de solubilisation de vanadium contenu dans l'asphalte a ete mise en evidence. Cette activite n'a ete obtenue qu'en presence de di-acetylacetonate de vanadyle dans le milieu liquide. Deux souches pures sauvages provenant des consortiums bacteriens ont modifie en culture pure une porphyrine de cuivre. Chacune des deux souches pures presentes egalement la capacite de demetalliser l'asphalte en colonne de percolation

La présence d'hétéroatomes et métaux dans des fractions lourdes de pétrole brut peuvent entraîner la désactivation des catalyseurs d’hydrotraitement et d’hydrocraquage. Les composés contenant ces éléments sont connus pour être inclus dans des agrégats macromoléculaires d’asphaltènes, qui sont considérées comme les composants les plus problématiques des produits pétroliers. Ces travaux ont pour objectif d’apporter une meilleure compréhension de l’environnement chimique de ces espèces et des phénomènes d’agrégation pour optimiser les processus de raffinage. Des techniques de séparation comme la chromatographie de perméation de gel ou Gel Permeation Chromatography (GPC), Advanced Polymer chromatographie (APC) et la chromatographie sur couche mince d’haute performance ou High Performance Thin Layer Chromatography (HPTLC) ont été combinées avec des techniques d’analyse élémentaire comme la spectrométrie de masse à plasma à couplage inductif ou Inductively Coupled Plasma Mass Spectrometry (ICP-MS) et la spectrométrie de masse moléculaire d’haute résolution pour la caractérisation des fractions pétrolières lourdes. Les profils de distribution en taille d’espèces qui contiennent du vanadium, du nickel et du soufre, les hétéroatomes et métaux les plus abondants dans les produits pétroliers, ont été déterminés par GPC couplé à une détection élémentaire par ICP MS. Les paramètres ayant le plus d’impact sur la distribution en taille et l’évolution des agrégats dans les solutions de différentes coupes pétrolières ont été optimisés. Cela nous a permis de faire différentes comparaisons, entre de nombreuses charges et effluents de procédés, ainsi que d’autres séries d’échantillons ou de mélanges provenant d’unités-pilotes d’hydrotraitement. Les résultats obtenus ont pu être mis en regard de caractéristiques macroscopiques comme la viscosité. Le couplage du nouveau système APC avec l’ICP MS a été mis au point avec succès. Cette technique a permis de réaliser des cartographies d’échantillons pétroliers plus rapides qu’en GPC tout en consommant moins de solvant. Cependant, les différences des chromatogrammes APC obtenus par rapport aux profils GPC suggèrent des interactions indésirables avec la phase stationnaire, qui ont été l’objet d’une évaluation approfondie.Enfin, un dernier type de séparation a été évaluée. L’HPTLC, qui utilise des plaques à usage unique, peut être appliquée à la séparation de produits lourds par polarité, et ce sans étapes de déasphaltage préalable, contrairement aux colonnes de chromatographie liquide qui peuvent être détériorées à cause de l'adsorption irréversible et de la précipitation des asphaltènes. Différents types de plaques et éluants ont été testés afin de développer une méthode simple pour la séparation des fractions SAR (Saturés, Aromatiques et Résines) des échantillons de distillat sous vide ou Vacuum Gas Oil (VGO). Ce travail avait pour but des migrations en une seule étape et analyse UV qui pourrait être mis en œuvre pour l’analyse de routine dans les laboratoires de contrôle avec une adsorption irréversible réduite. Des résultats très prometteurs ont été obtenus avec l’utilisation de plaques de cellulose pour la séparation des familles de polarité différentes au sein des agrégats d’asphaltènes. Des tests sur l'analyse directe des plaques par Désorption-Ionisation par Électronébulisation (DESI) MS, l'analyse directe en temps réel ou Direct Analysis in Real Time (DART) MS et Ablation Laser (LA) ICP MS ont été effectués
The presence of heteroatoms and metals in heavy fractions of crude oil can cause the deactivation of hydrotreatment and hydrocracking catalysts. Compounds containing these elements are known to be included in macromolecular asphaltene aggregates, which are considered the most problematic components of heavy oil. This thesis aimed for a better understanding of the chemical environment of these species and on the aggregation phenomenon to optimize refining processes. Separation techniques such as Gel Permeation Chromatography (GPC), Advanced Polymer Chromatography (APC) and High Performance Thin Layer Chromatography (HPTLC) were combined with elementary analysis techniques such as Inductively Coupled Plasma Mass Spectrometry (ICP MS) or high-resolution molecular mass spectrometry for the characterization of heavy fractions of crude oil. Here, the size profiles of species that contain vanadium, nickel and sulfur, the most abundant heteroatoms and metals present in petroleum products, were determined by GPC online with elemental detection by ICP MS. The parameters having the most significant impact on size distribution and the evolution over time of aggregates from solutions of different petroleum cuts were optimized. This allowed the comparison between various feeds and effluents and other series of samples and mixtures from pilot units of refining processes by GPC ICP MS. Results obtained could be related to macroscopic characteristics such as viscosity. Hyphenation of the new APC System to ICP MS has been successfully completed. It allowed the mapping of petroleum samples faster than GPC, therefore with less solvent consumption. However, the differences of the APC chromatograms obtained with respect to the GPC profiles suggested significant unwanted interactions of the highly polar compounds of the petroleum samples with the stationary phase, which have been thoroughly studied. Finally, another type of separation was evaluated. HPTLC, of single-use plates, can be applied to the analysis of heavy petroleum products by polarity without prior deasphalting steps while chromatography columns can be deteriorated because of the irreversible adsorption and asphaltene precipitation. To this end, various types of plates and eluents were tested to develop straightforward SAR (Saturates, Aromatics and Resins) separations of Vacuum Gas Oil (VGO) samples. This method, based on single-step migrations with reduced irreversible adsorption and UV monitoring, could be implemented for routine analysis in control laboratories. Very promising results were obtained by the use of cellulose plates for the separation of different families within asphaltene aggregates. Tests on Desorption ElectroSpray Ionization (DESI) MS, Direct Analysis in Real Time (DART) MS and Laser Ablation (LA) ICP MS analyses of the plates have been performed

L’exploitation des pétroles lourds, devenue populaire en raison des pénuries en réserves d’énergie, est rendue difficile par la présence de métaux lourds comme le nickel ou le vanadium, qui affectent les procédés de raffinage. L’objectif de cette thèse était de développer de nouvelles méthodes analytiques afin d’étudier la distribution de ces métaux dans le pétrole et ses fractions. Les principaux développements sont : (i) une méthode sensible permettant l’analyse directe de matrices organiques en ICP MS (ii) un couplage ente la chromatographie liquide à perméation de gel avec l’ICP MS, et (iii) un couplage ente la chromatographie de phase normale et l’ICP MS qui permet l’analyse 2D perméation de gel – phase normale de la distribution des métaux dans des fractions pétrolières par ICP MS. Les méthodes développées ont été appliquées pour l’analyse de plusieurs pétroles et de leurs fractions
The use of heavy petroleum, increasingly popular because of the shortage of energy supplies, is hampered by the presence of heavy metals, such as nickel and vanadium, which negatively affect refining processes. The objective of the thesis was to develop novel analytical methods able to study the metal distribution in petroleum, its fractions and related products. The principal developments include: (i) a high-throughput sensitive method for the analysis of organic matrices based on flow-injection total consumption micronebulisation ICP MS; (ii) a coupling of gel-permeation LC with ICP MS; and (iii) a coupling of normal phase LC – ICP MS allowing the 2D gel-permeation – normal phase characterization of the metal distribution by ICP MS. The methods developed were applied to the analysis of a number of crude oils and their fractions

Différents secteurs industriels génèrent, par an, des milliers de tonnes de catalyseurs usés contenant jusqu'à 35% de métaux de valeur comme Co, Cr, Cu, Ni, Mo, Ti, V, W, etc. , sur des supports composés d'alumine, de silico-aluminate, de dioxyde de titane, etc. Ces solides contiennent souvent des impuretés comme C, S, Fe, Pb, P, etc. Le recyclage des éléments économiques de ces déchets pourrait contribuer à la protection de l'environnement. L’objet de ce travail est d'extraire sélectivement le cobalt, le nickel, le molybdène et le vanadium des catalyseurs usés d'hydrodésulfuration de pétrole et d'obtenir un résidu final inoffensif pour l'environnement. La caractérisation physico-chimique de 30 échantillons provenant de trois pays européens a permis de les classer en 4 groupes majeurs. Des échantillons représentatifs de ces groupes ont été utilisés au cours de ce travail. Le grillage préalable, pour l'élimination des impuretés, a été optimisé. Après une analyse thermodynamique, la cinétique de chloruration et de carbochloruration des composés purs, des éléments majeurs de ces catalyseurs usés, a été étudiée. Les résultats ont servi comme base pour aborder la chloruration et la carbochloruration des catalyseurs usés. La chloruration sélective de ces échantillons par différents mélanges gazeux a été obtenue grâce au contrôle de la pression partielle d'oxygène, du temps et de la température. Les meilleurs résultats ont été obtenus par la chloruration des échantillons non grillés en employant un mélange chlore-air à des températures inferieures à 600°C. Plus de 90% des métaux de valeur sont extraits. Ces résultats ont été confirmés à l'échelle semi-pilote. Le résidu final est composé essentiellement d'alumine ou de silico-aluminate. Un schéma de traitement est proposé

Les défauts d'un cristal sont les porteurs de la diffusion. Le flux J des défauts ponctuels dans le volume du cristal et le flux J' des espèces diffusant dans les défauts étendus sont supposés parallèles dans notre modèle d'oxydation des métaux. La vitesse s’écrit v = J(1 - théta ) + J'théta , théta est la portion de l'aire occupée par les "courts-circuit" constitués par les défauts étendus du cristal. Ce modèle permet d'expliquer le comportement d'échantillons de nickel revêtus de V₂O₅ sous oxygène pur, à 900°C : La vitesse d'oxydation est maximale pour une pression d'oxygène de 20 kPa et proportionnelle à l'épaisseur du dépôt. L'étude morphologique (par diffraction RX en incidence oblique, spectroscopie Auger, M. E. B. ) montre qu'un composé oxygéné de nickel et de vanadium est localisé dans la couche de l'oxyde NiO. Tant que ce composé est liquide ou non-stœchiométrique, la corrosion est catastrophique, sinon la diffusion est bloquée et la vitesse inférieure à celle observée pour le nickel pur. A priori, un élément susceptible de réagir avec V₂O₅ pour former un solide peut protéger le matériau. Ainsi un revêtement de magnésium métallique sur le nickel ou sur un acier inoxydable (type 25-20) s'avère efficace.

The speciation of sulfur compounds in CAP is very important, considering that these compounds are responsible for oxidation processes in asphalt binders, modifying their chemical and physical characteristics. The aim of this work was focused on chemical speciation of sulfur compounds in virgin and aged CAP samples (methods RTFOT, RTFOT/PAV, and RTFOT/SUNTEST) and their maltenic fractions. The separation of sulfur classes were carried out using the method developed by Payzant, which employs specific oxidation reactions and chromatographic separation on silica columns. The studied sulfur compound classes were the following: aromatic/saturated sulfur, aliphatic sulfides, thiophenes and sulfoxides. For this purpose, 6 samples were comparatively analyzed in virgin and aged CAP regarding the distribution of sulfur compounds in the three obtained fractions, where total sulfur was determined in order to observe the compounds behavior in the fractions after different aging processes. After speciation of the compounds, it was observed that the aging process occurs with structural changes in CAP, which involved the break and opening of thiophenic rings and the consequent formation of new S-compounds of high molecular weight. Sulfur compounds in form of sulfoxides increased after aging by RTFOT and RTFOT/PAV. Nickerl and vanadium were also analyzed in the studied samples by GFAAS (maltenic and asphaltenic fractions), since these species are involved in the aging process in CAP. The distribution of Ni and V in asphaltenic and maltenic fractions showed a diminishing of contents of the metals due to the lost by volatilization as metalloporphyrins. Correlating the chemical and physical changes observed in CAP, the variation in viscoelastic properties (G*/sin) may be a reflect of alterations in thiophenic fractions; additionally, variations in the penetration point may be related with the variation in asphaltenes and sulfur compounds of acid/basic characters, what may also be related to the viscoelastic changes in CAP. Based on the obtained results, this work aimed to answer 6 main guiding questions of the thesis: (1) which transformations occur in the speciation of sulfur compounds with the CAP aging after short-term, long-term and UV radiation processes?; (2) what is the major class of sulfur compounds in CAP and how it changes with the aging process?; (3) which transformations occur in the metals nickel and vanadium with CAP aging after short-term, long-term and UV radiation processes?; (4) the forced aging processes for CAP (RTFOT, PAV and SUNTEST) lead to different chemical transformations in asphaltenes and maltenes?; (5) what are the correlations existing between the chemical and physical changes in CAP, from the chemical speciation and rheology after aging process?; (6) is it possible to establish some chemical reactivity order for CAP based on the chemical speciation and rheology after aging process?
A especiação de compostos sulfurados em CAP é de grande importância, uma vez que alguns desses compostos são responsáveis pela oxidação de ligantes asfálticos, modificando suas características químicas e físicas. Este trabalho tem como foco a especiação química de classes majoritárias de compostos sulfurados em amostras de CAP virgem e envelhecidas (métodos RTFOT, RTFOT+PAV e RTFOT+SUNTEST) e suas respectivas frações maltênicas. A especiação das classes sulfuradas foi realizada pelo método adaptado de Payzant empregando reações de oxidação específicas e separações cromatográficas por adsorção em sílica. Os teores de sulfóxidos foram obtidos por FTIR, utilizando-se como padrão de sulfóxidos uma solução de referência de tetrametileno sulfóxido (TMSO) em diclorometano. As classes de compostos estudadas foram: sulfurados aromáticos/saturados, tiofenos, sulfetos alifáticos e sulfóxidos. Para isso, foram analisadas comparativamente 6 amostras de CAP virgem e envelhecidas em relação à distribuição dos compostos sulfurados nas três frações obtidas, onde foram analisados os teores de enxofre total a fim de se observar o comportamento dos compostos nessas frações nos diferentes processos de envelhecimento. Com base nesses resultados, observa-se que no processo de envelhecimento ocorrem mudanças estruturais envolvendo quebras de ligações em anéis tiofênicos e formação de novas classes de compostos sulfurados de maior peso molecular. Os compostos de enxofre na forma de sulfóxidos apresentaram um aumento decorrente dos processos de envelhecimento para os envelhecimentos RTFOT e RTFOT/PAV. Também foram analisados os teores de Níquel e Vanádio nas diferentes amostras, em suas frações maltênicas e asfaltênicas por GFAAS, já que estes metais são envolvidos como coadjuvantes no processo de envelhecimento dos CAPs. A distribuição dos metais de Ni e V nas frações asfaltênicas e maltênicas sofreu uma diminuição nos teores destes metais decorrente das perdas por volatilização na forma de metaloporfirinas. Correlacionando-se as alterações químicas e físicas observadas em CAP, as variações nas propriedades viscoelásticas (G*/sin) podem ser um reflexo das alterações que ocorrem nas frações tiofênicas; além disso, a variação no aumento da penetração pode estar relacionada com a variação do teor de asfaltenos e de compostos de caráter e básico, que também podem ser relacionados com as mudanças viscoelásticas dos CAPs. Com base nos resultados obtidos, esse trabalho buscou responder a 6 perguntas principais e norteadoras da tese apresentada: (1) que transformações ocorrem na especiação de compostos de enxofre com o envelhecimento de CAP em curto prazo, longo prazo e sob ação da radiação UV?; (2) qual a classe majoritária de compostos de enxofre em CAP e como esta se altera com o envelhecimento?; (3) que transformações ocorrem nos metais níquel e vanádio com o envelhecimento de CAP em curto prazo, longo prazo e sob ação da radiação UV?; (4) os processos de envelhecimento forçado de CAP (RTFOT, PAV e SUNTEST) conduzem a transformações químicas diferentes em asfaltenos e maltenos?; (5) quais as correlações existentes entre as transformações químicas e físicas em CAP, a partir da especiação química e da reologia após o envelhecimento?; (6) é possível estabelecer alguma ordem de reatividade química para o CAP com base na especiação química e na reologia após o envelhecimento?

Le présent travail concerne l’étude par simulation numérique, basée sur les équations de diffusion microscopique d’Onsager, du vieillissement isotherme d’alliages intermétalliques à partir de l’état désordonnée. On s’intéresse en particulier au phénomène de coalescence dans les alliages Ni-Al, Ni-V et Ni-Al-V. L’effet des interactions élastiques est pris en compte dans le modèle. Premièrement, le modèle a été testé sur l’alliage Ni-Al. On montre que les données issues de la simulation sont cohérentes avec celles de la littérature. Deuxièmement, nous avons étudié l’alliage Ni-V. Nos simulations reproduisent la microstructure monovariant qui a été observée expérimentalement. De plus, on a regardé l’influence du défaut d’ajustement cristallin (misfits) sur la stabilité de la microstructure bi-variant. Enfin, nous étudions l’alliage Ni-Al-V. Nous montrons qu’il est possible, dans le cadre de notre modèle, de reproduire la microstructure complexe dans les alliages ternaires
In this work, the kinetics of isothermal ageing in intermetallic systems were studied using a computer simulation technique based on Onsager microscope diffusion equations. In particular, our focus is on the coarsening kinetics in Ni-Al, Ni-V and Ni-Al-V alloys. To reproduce the microstructures in Ni-based alloys, the elastic interactions were taken into account in our model. First, the model was applied for Ni-Al alloy. Our results are in good agreement with recent experimental observations and simulations results. Then Ni-V alloy was studied. It was shown that our simulations reproduce the experimentally observed monovariant microstructure in this system. The influence of the lattice misfits on stability of two-variant microstructure was demonstrated. Finally, Ni-Al-V alloy was studied. Simulation results showed that proposed model is able to reproduce the complex microstructure in ternaries alloys

This research measured particle and gaseous emissions from ships and trains operating within the Port of Brisbane, and explored their influence on ambient air composition at a downwind suburban measurement site. The ship and train emission factor investigations resulted in the development of novel measurement techniques which permit the quantification of particle and gaseous emission factors using samples collected from post-emission exhaust plumes. The urban influence investigation phase of the project produced a new approach to identifying influences from ship emissions.

This thesis aims to assess the extent of contamination of soil and sediment with risk metals in Jelšava. The main polluter of the environment in this area is the magnetize factory. Sampling of soils and sediments were made in three seasons. Sampling times were staggered to represent different seasons and to take into account the impact of the seasons on the obtained values of the concentrations in soil and sediment. Sampling sites were selected according according to the different distances from the factory and according to the different loading of roads. In each of the collected samples were determined concentrations of the elements copper, lead, zinc, nickel, manganese, mercury, cadmium and vanadium. Copper, lead, zinc, nickel and manganese were analyzed by atomic absorption spectrometry with atomization in a flame (F AAS), cadmium and vanadium were determined by atomic absorption spectrometry with electrothermal atomization (ET AAS). For the determination of mercury was used mercury analyzer (AMA).

Ce memoire est consacre a la synthese, la structure et la conductivite de bi#4v#2o#1#1 et de ses substitues (cu, ni). La phase haute temperature (gamma) de bi#4v#2o#1#1 est fortement conductrice d'anions oxygene. La substitution partielle du vanadium par le cuivre ou le nickel a tendance a stabiliser cette phase a temperature ambiante. Nous obtenons alors des composes bons conducteurs a basse temperature. La synthese de monocristaux et de poudres a permis de caracteriser avec precision la structure et la conductivite de ces materiaux. Nous avons mis en evidence l'influence des protocoles de synthese sur la symetrie et la conductivite, ainsi que l'existence de transition a cinetique tres lente. Nous avons egalement observe l'anisotropie de la conductivite liee a la structure en couches des materiaux. Les structures des deux phases hautes temperature (beta et gamma) de bi#4v#2o#1#1 ainsi que du compose substitue au cuivre a 12,5% ont ete etudiees par diffraction des rayons x et des neutrons. Cette etude a permis de proposer plusieurs modeles de diffusion microscopique des anions oxygene. Un ordre apparaissant sur les environnements des ions vanadium permet d'expliquer la chute de conductivite lors de la transition de phase gamma beta. L'etude par absorption x au seuil du vanadium montre que son environnement n'est pratiquement pas affecte lors de la substitution par le cuivre. Et nous suggerons que l'augmentation de conductivite par substitution du vanadium provienne essentiellement de phenomenes d'ordre et de desordre sur l'environnement du vanadium

Neste trabalho foi feito o estudo sobre o efeito de elementos microligantes na composição química, microestrutura e propriedades mecânicas de metais como soldado produzidos por arco submerso com adição de pó de ferro em aço de alta resistência e baixa liga (ARBL). Foram feitos dois cordões de solda utilizando os aços BS - 4360 - 50 e USI - SAC - 50, o arame EM - 12K, o pó de ferro ESAB 400 e o fluxo experimental 10.71P. Utilizando-se a corrente de 600 A, tensão de 34 V, velocidade de soldagem de 30 cm/min e vazão de pó de ferro de 6,7 Kg/h foram produzidos os metais como soldado com um único passe e chanfro em \"V\", que mostraram características de boa temperabilidade e estrutura refinada. O microconstituinte em maior porcentagem nos dois cordões de solda foi a ferrita acicular. Os ensaios mecânicos realizados foram a dureza, tração e impacto. O cordão de solda com nióbio e vanádio obteve maiores valores de dureza e resistência à tração em relação ao cordão com cobre, cromo e níquel. Entretanto os altos teores de manganês presentes fizeram com que o endurecimento por solução sólida reduzisse significativamente a resistência ao impacto dos dois cordões de solda. A natureza das inclusões não metálicas foi investigada por microscopia eletrônica e análise por EDAX.
The study of the effect of microalloying elements in the chemical composition, microstructure and mechanical properties of the as-welded metaIs obtained by submerged are welding with iron powder addition in High Strength Low Alloy (HSLA) steel were done. Two weld metaIs were made using, BS - 4360 - 50 and USI - SAC - 50 steels, EM - 12K wire, ESAB 400 iron powder and 10.71P experimental flux. Using welding current of 600 A, arc voltage of 34 V, travel speed of 30 cm/min and iron powder flow of 6,7 Kg/h were obtained as-welded metals by single pass into V - groove, that showed good hardenability and refined microstructure. The higher percentage microstructure in the two weld metals was the acicular ferrite. The mechanical tests done were hardness, tensile strength and impact. The weld metal with niobium and vanadium achieve better values of hardness and yield strength than with copper, chromium and nickel weld metal. However, the hardening by solid solution, induced by the high levels of manganese, decreased the impact strength of the two weld metaIs. The non - metallic inclusions nature was investigated by electronic microscopy and EDAX analysis.

Le but de ce travail est de fournir des informations qui peuvent aider à clarifier le mécanisme par lequel se produit la précipitation d’asphaltènes afin d'optimiser les modèles qui prédisent ce phénomène. Premièrement, la composition chimique des fractions aromatiques et saturées est analysée au regard à la stabilité des asphaltènes dans le brut. Plus précisément, la composition SARA de différents bruts vénézuéliens est corrélée au seuil de floculation des asphaltènes. Nos résultats mettent en évidence que les saturées, semblables aux résines, ont un effet significatif sur la stabilité des asphaltènes dans le brut. Deuxièmement, la teneur en Ni et V dans les asphaltènes et leurs sous fractions A1 et A2 a été déterminé par spectroscopie d'émission atomique avec plasma inductif. Les données expérimentales établissent que A1 a une concentration en V et en Ni supérieure à celle de A2, quelque soit la stabilité des bruts. Nous interprétons ces données comme l’illustration d’interactions fortes, telles que des liaisons covalentes entre pétroporphyrines et les molécules d’asphaltènes. Finalement, un dispositif haut pression est utilisé pour détecter visuellement la pression seuil de floculation d'un système modèle correspondant à une solution d’asphaltènes dans un mélange toluène/heptane/CO2. Les résultats confirment, pour ces systèmes gazés, que les augmentations de pression conduisent à une augmentation de la solubilité des asphaltènes et que pour la température il y a deux régimes opposés. Le premier correspond à une diminution de la stabilité du fluide avec l’augmentation de la température et le second, passé une valeur seuil proche de 80°C, conduit au phénomène inverse
The purpose of this work is to provide information that can help in clarifying the mechanism by which asphaltene precipitation occurs in order to optimize the models that predict the phenomenon. The study is divided into three chapters. In the first one, the constituents of aromatic and saturate fractions of some Venezuelan crude oils were associated with the asphaltenes stability. SARA composition was correlated with asphaltene flocculation onsets and the results showed that saturates, similar to resins, have a significant effect on the flocculation process of the asphaltenes. In the second chapter, the concentration of Ni and V was determined in asphaltenes and their fractions A1 and A2. The samples were analyzed using inductively coupled plasma atomic emission spectrometry and elemental combustion analysis. Results show that A1 presents higher Ni and V concentrations than A2, in both stable and unstable crude oils. These results can be explained by strong interactions, such as covalent bonds between the petroporphyrins and the asphaltene molecules. In the final section, the asphaltenes phase envelopes were obteined for a system consisting of asphaltene in a mixture toluene/heptane/CO2. The temperature ranges 10-150 °C with varying concentrations of CO2 between 10 and 20 wt%. The experimental results confirm that increase of pressure leads to increase of solubility of the asphaltenes in the medium. Also, there are two temperature regimes having opposite trends. First, the solubility of the asphaltenes increases with the temperature, then after a threshold value of 80 °C, the stability is getting worse with the temperature

碩士
國立成功大學
資源工程學系碩博士班
101
It is estimated that more than 13,000 tons of spent hydrodesulfurization catalysts are annually generated in Taiwan, which contains valuable metals like cobalt, molybdenum, nickel, vanadium, etc. If the spent hydrodesulfurization catalysts are disposed directly, the released metals may cause a secondary pollution of the environment. In this study, the spent hydrodesulfurization catalysts were first processed by a thermal pretreatment, and its effects were determined by TOC and XRD analysis. Results of TOC analysis that preheating in higher temperature and longer time will indicated the oil and tar on the surface of spent hydrodesulfurization catalysts were completely removed. The results of XRD analysis confirmed that preheating the samples at 600℃ for 5h provides enough energy to induce an oxidized roasting reaction in samples which transforms the sulphides into oxide. Next, the extraction of nickel, vanadium and molybdenum from spent HDS catalysts by using the sulphtization roasting-leaching process and direct acid leaching process was discussed. The result indicated that the best conditions for nickel, vanadium and molybdenum extraction were: thermal pretreatment at 600℃ for 2h, spent HDS catalyst/ NaHSO4•H-2O(s) mixed mass ratio of 1/7.5, acid roasting temperature of 600℃, acid roasting time of 1h, leaching solution of 3N H2SO4(aq), leaching temperature of 70℃ and leaching time of 30min. The final extraction rate for vanadium, nickel and molybdenum were 100%, 91.2% and 90.6% respectively. Finally, extraction of vanadium, nickel and molybdenum using direct acid leaching method consume much more sulfuric acid than using the sulphtization roasting-leaching method.

碩士
崑山科技大學
電機工程研究所
104
In this study, RF sputtering deposition of vanadium pentoxide films on ITO glass substrate, as well as RF magnetron co-sputtering deposition of nickel-doped vanadium pentoxide on the ITO glass substrate film were investigated. The films were obtained by changing process time, argon and oxygen pressure ratio and different annealing temperatures. Then in order to investigate the optical properties between the therefore,the film of vanadium pentoxide and nickel doped vanadium pentoxide doped, compositional analysis and electrochromic properties were be determined by cyclic voltammetry, X-ray diffraction, FE-SEM, UV-visible spectrometer, atomic force microspoic and auger electron spectroscopy. Experimental results indicated that the electrochromic properties show significantly higher than other low-time films manufacturing process at non-oxygen,3hrs process time and film thickness of 288.2nm. The transmittance change between colored and bleached states at a wavelength of 600nm was 25.6% because of a larger circulation area as well as a larger capacity. When the argon and oxygen pressure ratio was 15: 1,the vanadium pentoxide films obtained the best electrochromic properties. The transmittance change between colored and bleached states at a wavelength of 600nm was 43.8%. The films show a significant Redox peaks under cyclic voltammetry analysis. The peaks improves the transmittance difference at colored and bleached states. After the vanadium pentoxide thin films processed through different temperature annealing,the flim is crystallized at 400℃ annealing,however,the film annealed at 300℃ has better electrochromic performance than no annealed. The transmittance change between colored and bleached states at a wavelength of 600nm was 28.7% and the films appear a reduction peak under cyclic voltammetry analysis. Nickel-doped vanadium pentoxide film was deposited at fixed time of 2hr by sputtering. When the doping power is 30W, nature properties of the thin film has a little bit of change. Then when the doping power is above 50W, because nickel content in thin film is more. The effect was deepen the vanadium pentoxide thin film in the anode color. The result indicates that the films change its color form anode coloration turn to cathodic coloration observed from the change of a whole circulation volt-ampere graph. When the doping power was 80W , the best electrochromic properties obtained. The transmittance change between colored and bleached states at a wavelength of 600nm was 35.2%. When the nickel-doped power is 10W, the best film electrochromic properties was gotten at the argon and oxygen pressure ratio of 15:1. Then the transmittance change between colored and bleached states at a wavelength of 600nm was 25.6% and 9.5% retaled to nickel doped vanadium pentoxide and undoped films. That result indicated the doped with a small amount of nickel can actually improve the electrochromic properties of vanadium films.

碩士
國立臺北科技大學
車輛工程系所
96
Electrochromic technology has been widely used for general applications to daily life. Novel development of electrochromic system has been made on the applications of automobile windshield and architecture windows. The smart windows can modulate light flux and control heat loadings. Applications on low power monitor or specialty filters also provide solutions for energy and cost cut. In this study, the valence mixture of nickel in Ni-V oxide films appears to affect the change of transmission rate (△T) more than oxygen concentration in the oxide thin films. The concentration of +2 and +3 valence mixture increases coloration efficiency. Films made by an optimum sputtering working atmosphere of 66.67% oxygen content demonstrate coloration efficiency of CE= 32.03 cm2/C at 550nm wavelength. After annealing at 400℃, oxygen content in the film appears to reduce. The optical band gap also reduces from 3.99eV to 3.89eV. It is proposed that the increase of oxygen vacancies causes the valence band and conduction band to approach and thus narrow the optical band gap.

D. Tech. Environmental, Water and Earth Sciences
Pollution of water sources with heavy metals is currently a global concern due to the detrimental effect of these metals on both human and animal health. To address this issue, biological treatment methods have been seen as the most effective and eco-friendly option of the available treatment processes of wastewater. The aim of this study was to compare the ability of selected bacterial isolates and indigenous protozoan to tolerate nickel and vanadium in wastewater systems in order to determine which group of organisms might play a major role in the removal of nickel and vanadium, even at high concentrations, in wastewater treatment systems.

碩士
國立金門大學
電子工程學系碩士班
107
The electrochromic film is applied to the windows of a building. When the outdoor sunlight is strong, the color of the window can be changed by controlling the potential or current, and the intensity of the sunlight passing through the window can be controlled at will and the heat is blocked. The purpose of regulating and reducing heat load is achieved to reduce energy waste. In addition to process limitations, the adhesion between electrode elements is weakened, the corrosive effect of acidic liquid electrolytes, long-term intense light irradiation, high temperature environment, electrolyte deterioration and liquid leakage, etc., all of which result in short service life and low optical density of electrochromic materials. And the reason for the slow coloring, and the auxiliary electrode nickel oxide is magnetic, requires special equipment to prepare, and is not easy to be widely used. This study proposes that the Taguchi method optimizes the electrochromic film combined with the intelligent control system, which not only solves the magnetic problem of nickel oxide. Through the integration of the Taguchi method and the rule of thumb, it is possible to greatly reduce the number of experiments and find the optimum process parameters for preparing the nickel-vanadium oxide film. According to the prediction analysis of Taguchi method, the S/N ratio is 8.20 when the original parameter sputtering power is 150W and the oxygen flow rate is 1sccm. The optimized parameter 100W 20sccm can reach the S/N ratio of 28.80, and the difference is nearly 20.60. According to XRD, SEM, electrochromic properties and optical analysis, JCPDF cards 47-1049、01-1260 and 89-7129 show that the Ni2O3 film has a polycrystalline structure, preferred orientation is Ni2O3 (111). Microstructural results show that when the oxygen flow increases, the target poisoning phenomenon will occur, resulting in a significant decrease in the deposition rate, but the surface density will be more dense. The thickness of the film is proportional to the power, inversely proportional to the oxygen flow, and the surface density is proportional to the oxygen flow. The optical analysis showed that the optimized nickel oxide vanadium film ultraviolet light (400nm), visible light (550nm), infrared light (800nm) optical modulation (ΔT) were 25.1%, 38.7%, 32%, respectively. The optical density (ΔOD) was 0.478, 0.375, and 0.249, respectively, and the coloring efficiency (CE) was 24.475, 19.201, and 12.45. Since this study is an auxiliary electrochromic layer, the electrochromic layer can be used to make up for the unstoppable light, so it is possible to find a path to find the electrochromic film with the best fading effect, and make an all-solid electrochromic film. When it is not only able to solve the problem that the nickel-vanadium oxide film cannot have both high optical modulation effect and high fading efficiency. From the results, the best parameter is 300W oxygen flow rate 20sccm. The optical modulation of ultraviolet light (400 nm), visible light (550 nm), and infrared light (800 nm) at the time of fading was 75.8%, 80.8%, and 83%, respectively, and the full spectrum was as high as 75% or more. Finally, this study will optimize the nickel oxide vanadium electrochromic film combined with the fuzzy PID control system. Through this system, the light of up to 1000Lux can converge the light illumination to the CNS standard indoor illumination of 500Lux in 8 minutes. Achieve effective control of indoor ambient light, solve the shortcomings of traditional curtains that cannot control sunlight. And the results confirmed that it can effectively block the main thermal energy infrared light in the sun, indoor blocking nearly 81.98% of infrared light, and reduce the indoor temperature from 30 degrees to 26 degrees. The research uses the Taguchi method combined with the optimization of the nickel-vanadium oxide film experiment, which can reduce the number of experiments in the traditional process, and can better combine the researcher's rule of thumb to achieve more effective optimization of the film. The results show that the Taguchi method can not only quickly find the best parameters of the process, but also effectively optimize the electrochromic film. And this study combines fuzzy PID control system. This system does not require cumbersome and high-cost hardware equipment, can achieve the purpose of regulating and reducing indoor temperature and visible light, and can reduce the energy consumption of indoor air conditioners, and achieve energy saving and carbon reduction effects.

Filter Cake, which contains leachable nickel and vanadium above the criteria in the Alberta Waste Control Regulation, is produced at an oil sands facility operated by Nexen Inc. and is currently being disposed in a landfill. Bench scale and field tests were performed with stabilization/solidification (S/S) treatment reagents such as Portland cement, fly ash, elemental sulphur, and CETCO Oilfield Service’s proprietary reagents to assess their efficacy at reducing leachable metals in Filter Cake. The CETCO reagents were the most effective treatment for reducing leachable nickel and vanadium in Filter Cake. Treatments with Portland cement were successful in bench scale tests, but inconsistent in field tests. The inconsistent results obtained for Portland cement may have been due to interferences of the cement reactions from factors such as fine particulates. S/S treatments of Filter Cake present a viable waste management option. However, the associated reduced cost and environmental impacts were not substantial.

碩士
國立中央大學
材料科學與工程研究所
101
In this study, the electrodes were prepared by electrochemical manner. In the beginning, porous nickel substrate was prepared by alloy/dealloy method in an aqueous solution containing Cu(II) and Ni(II). This material has high specific surface and uniform structure, very suitable for electrical storage devices as current collector. The first study, vanadium oxide deposited on porous Ni and explored its capacitance characteristics in 3 M KNO3 electrolyte. A porous nickel substrate compared to flat substrates, which can proof nanostructures greatly increase their capacitance value and improve the maintenance at high rate, low internal resistance leading to the overall performance significantly enhanced. The 2nd study is lithium batteries fabrication, the most widely used energy storage components. Using porous nickel with tin electrode, the absolute expansion will effectively reduce and the uniformity structure of the substrate can avoid concentration of stress. Between two kind substrates, the porous substrate exhibited higher capacitance value at high current density (15 A g-1), the capacity reached 459 mAh g-1. Although applying nano substrate is a possible way, the ionic liquid is used as the plating solution can directly deposited nanostructures give the better method. In details for the ionic liquid system, without the side reaction of electrolysis of water, the deposition efficiency can be greatly improved for further industry processes, the utilization of ionic liquid will avoid oxides and other byproducts generated in long waiting time. At the first cycle, the lithiated capacity is 863 mAh g-1 and the reversible capacity is 641 mAh g-1 (0.3 A g-1), which is comparable to those prepared in aqueous solution.

Το ηλεκτροπαραγωγικό δυναμικό της ΔΕΗ περιλαμβάνει άνω των 40 πετρελαϊκών σταθμών συνολικής ισχύος 2100MW και οι μεγαλύτεροι είναι του διασυνδεδεμένου συστήματος και λειτουργούν στο Λαύριο και το Αλιβέρι. Οι υπόλοιποι λειτουργούν στο αυτόνομο σύστημα των νησιών του Αιγαίου και Κρήτης. Κατά τους καθαρισμούς των προθερμαντών αέρος και των δεξαμενών μαζούτ των μονάδων αυτών παράγονται σήμερα άνω των 500t στερεών καταλοίπων ετησίως με αυξητική τάση. Τα κατάλοιπα αυτά χαρακτηρίζονται σύμφωνα με την Ευρωπαϊκή οδηγία ως επικίνδυνα. Σύμφωνα με τους κανονισμούς της Ε.Ε. είναι υποχρεωτική η αδρανοποίησή τους και η διασφάλιση της ασφαλούς τους απόθεσης. Στα πλαίσια της παρούσας διατριβής πραγματοποιήθηκε πλήρης χαρακτηρισμός προεπεξεργασμένων και μη στερεών καταλοίπων. Προσδιορίστηκε ότι τα κατάλοιπα αυτά περιέχουν 1.6-13.4%V και 0.8-5.5%Ni, δηλαδή αποτελούν πολύ πλουσιότερες πρώτες ύλες από τα αντίστοιχα κοιτάσματα μεταλλευμάτων βαναδίου και νικελίου. Για παράδειγμα τα Ελληνικά νικελιούχα σιδηρομεταλλεύματα που καμινεύονται στη Λάρυμνα έχουν περιεκτικότητα μόλις 0.93-1.02% σε νικέλιο. Δεν ανιχνεύθηκε οργανικό φορτίο στα κατάλοιπα και το βανάδιο εντοπίστηκε σ’ αυτά στη μορφή VO2. Βασικός στόχος της διατριβής ήταν η ανάπτυξη μεθόδου, που να συνδυάζει την αδρανοποίηση των καταλοίπων με την ανάκτηση των περιεχόμενων μετάλλων. Η μέθοδος περιλαμβάνει και στάδιο πυροσυσσωμάτωσης των ανεπεξέργαστων καταλοίπων, στοχεύοντας στη συσσωμάτωση και εμπλουτισμό τους στα πολύτιμα κραματικά μέταλλα. Εξασφαλίζεται παράλληλη αποθείωση, απανθράκωση και ξήρανσή τους. Τα συσσωματώματα περιέχουν μέχρι και 6.0% Ni και 14.7% V, δηλαδή επιτυγχάνεται ο εμπλουτισμός τους κατά 8% σε Ni και κατά 10% σε V, με ταυτόχρονη απομάκρυνση θείου και άνθρακα σε ποσοστά 73 και 85% αντίστοιχα. Η πυροσυσσωμάτωση λειτουργεί ως αυτογενής διεργασία με την πλήρη ενεργειακή εκμετάλλευση της χημικής ενέργειας του άνθρακα και του θείου. Αποτελεί δε ταυτόχρονα το πρώτο βήμα για την ανάκτηση των περιεχόμενων μετάλλων. Συνακόλουθα, η εξασφάλιση ασφαλούς απόθεσης των αδρανοποιημένων και iii εμπλουτισμένων στα πολύτιμα μέταλλα καταλοίπων δίνει τη δυνατότητα δημιουργίας σοβαρού αποθέματος σωρεύοντας υλικό από το εσωτερικό αλλά και εισάγοντας παρόμοιου τύπου κατάλοιπα από ομοειδή εργοστάσια του εξωτερικού. Έτσι μια μεταλλουργική μονάδα ανάκτησης των μετάλλων θα μπορεί να εξασφαλίζει τη λειτουργία της με οικονομικότητα. Η εκτίμηση των επιπτώσεων της υπαίθριας απόθεσης των μελετούμενων στερεών αποβλήτων και των πυροσυσσωματωμάτων αποτελεί αδήριτο ανάγκη. Προς τούτο πραγματοποιήθηκε προσομοίωση της διεργασίας της έκπλυσής τους από τα όμβρια ύδατα. Το μοντέλο με την υπόθεση του μη αντιδρώντος πυρήνα, φαίνεται να περιγράφει με επαρκή ακρίβεια τη διεργασία. Οι σταθερές και ο πλήρης μηχανισμός του μοντέλου προσδιορίσθηκαν και επιβεβαιώθηκαν πειραματικά. Κατά την έναρξη της διεργασίας φαίνεται ότι η χημική αντίδραση αποτελεί το ρυθμορυθμιστικό βήμα για τη μεταφορά των μετάλλων στην υγρή φάση. Με την πρόοδό της έκπλυσης ελέγχεται από φαινόμενα διάχυσης. Την πρακτική εφαρμογή των μοντέλων που καταστρώθηκαν αποτέλεσε η πρόβλεψη των μακροχρόνιων επιπτώσεων της υπαίθριας απόθεσης των ανεπεξέργαστων και πυροσυσσωματωμένων καταλοίπων. Φάνηκε ότι απαιτείται μεγάλο χρονικό διάστημα, κατ’ ελάχιστο 10 έτη για την μείωση των συγκεντρώσεων των μετάλλων σε επιτρεπτά επίπεδα στον υδροφόρο ορίζοντα. Το τελευταίο στάδιο της προτεινόμενης μεθόδου περιλαμβάνει την αναγωγική τήξη των καταλοίπων. Πραγματοποιήθηκε σειρά πειραματικών χυτηρίων σε χωνευτήριο γραφίτη σε κάμινο Tammann. Μελετήθηκε η διεργασία αναγωγής των μεταλλοξειδίων καθώς και προσδιορίσθηκε η θερμοδυναμική ισορροπία των ετερογενών δράσεων μεταξύ ρευστής σκωρίας και μετάλλου σε θερμοκρασίες 1375-1600οC. Προσδιορίσθηκαν πειραματικά οι θερμοδυναμικές συναρτήσεις ισορροπίας για τα μεταλλοξείδια του βαναδίου, σιδήρου και νικελίου. Τα πειραματικά χυτήρια έδωσαν τελικούς βαθμούς ανάκτησης μετάλλων 85-98% για το Ni και 78-95% για το V, με παράλληλη παραγωγή αδρανοποιημένης σκωρίας κατάλληλης για απόθεση ή άλλες χρήσεις. Οι συνθήκες οι οποίες μεγιστοποιούν τις ανακτήσεις των Ni και V όπως έδειξαν οι πειραματικές δοκιμές είναι:  υψηλές θερμοκρασίες  χρήση χωνευτηρίου γραφίτη iv  προσθήκη σιδηροπυριτίου ως αναγωγικού μέσου Αντίθετα από την επικρατούσα άποψη, αποδείχθηκε, ότι επιτυγχάνονται υψηλοί βαθμοί ανάκτησης σε υψηλά επίπεδα βασικότητας CaO/SiO2>2, κάτι, που εξασφαλίζει την πυρίμαχη επένδυση της καμίνου και την περαιτέρω χρήση της παραγόμενης σκωρίας. Εναλλακτικά, μελετήθηκε και η απευθείας αναγωγική τήξη των φυσικοχημικά προεπεξεργασμένων καταλοίπων. Σημαντικό είναι το εύρημα, ότι η προσθήκη βωξίτη βοημιτικού τύπου σε μικρά ποσοστά προσθηκών μέχρι 10% δρα ενισχυτικά στις ανακτήσεις του νικελίου και του βαναδίου με βαθμούς ανάκτησης άνω του 98%. Διερευνήθηκαν επίσης η κινητική της αναγωγής των οξειδίων του σιδήρου και του βαναδίου από την σκωρία στο λουτρό σιδήρου και προσδιορίστηκαν οι αντίστοιχες σταθερές και τα ρυθμορυθμιστικά βήματα. Συνολικά, προτείνεται μια ολοκληρωμένη μέθοδος ανακύκλωσης των στερεών καταλοίπων πετρελαϊκών σταθμών παραγωγής ενέργειας σε συνδυασμό με υψηλότατους βαθμούς ανάκτησης των περιεχόμενων σε αυτά πολύτιμων κραματικών στοιχείων νικελίου και βαναδίου αποφεύγοντας την εξουδετέρωσή τους με ακριβές μεθόδους αδρανοποίησης. Με αυτόν τον τρόπο εξασφαλίζεται η εξουδετέρωση των επικίνδυνων αυτών υλικών με σημαντικά οικονομικά οφέλη από την ανάκτηση των μετάλλων.
The power generating installations of P.P.C. include m ore than 40 oil-fired power stations of about 2100MW total capacity. The mos t important stations are those of the interconnected system that ope rate in L avrio and Aliv e ri. The rest operate in the autonom ous system of the A eg e an islands and Cre te . M ore than 500t of solid w aste s are produce d annually during the w ashing proce sses of the air pre -he aters and the crude oil tanks of the aforementioned units w ith increasing te nden cy. These residue s are classifie d as hazardous according to the Europe an directive s. The ir neu tralizati on and safe de position is c om pulsory according to the E.U. re gulations. In the current the sis, complete characte rization of pretre ate d and untre ated re sidues was carried out. It w as found that the re sidues exa mined contained 1.6-13.4 %V and 0.8-5.5%Ni, being the refore a conside rably richer raw material than the vanadium and nickel ore deposits. For instance, the H elle nic nicke lferrous ore s, that are smelted in L arym na contain only 0.93-1.02% Ni. No organic compounds w ere de te cte d in the re sidues and the presence of vanadium was identified as VO 2. The fundam ental task of the thesis w as the de ve lopment of a method that com bine s the neutralization of the re sidue s with the recovery of the me tals containe d. The propose d me thod includes also a sinte ring stage of the untre ated residues, aiming at their agg lom e ration and e nrichm e nt in the pre cious alloying metals. The re sidues de sulphurization, de carburization and drying is achieved sim ultaneously. The sinter products contain up to 6.0% Ni and 14.7 % V, sugge sting that en richment of 8% in N i and 10 % in V w as achiev ed, with simultaneous loss of sulphur and carbon in the rates of 73 and 85% respe ctive ly. S inte ring, acts as an indigen ous process with total exploitati on of the che mical en e rgy of carbon and sulphur. It also rep re sents the first ste p for the re covery of the m etals containe d in the residues. Mo reov e r, provided the safe depo sition of the neutralize d and en riche d in valuable m e tals re sidue s, it is possible to ge ne rate a significant stock by piling m aterial from the indige nous sou rce s and imports of such residues. Thus a me tallurgical unit of m e tals re covery could operate at profit. The e valuation of the effects of the ground disposal of the investigate d solid re sidue s and sinte r produ cts is a mus t. The simulation of their le aching by rainfall wa s thus vii conducted. The hypothesis of the unreacted core mode l see ms to describe the proce ss ade que ntl y. The mode l constants and its complete m e chanism we re de te rmined and confirm ed expe rimentall y. Initially chem ical re action se ems to be the rate-de te rmining ste p for the transfe r of me tals in the liquid phase. W ith the e lution prog re ss the me chanism is controlled by diffusion phenomen a. The prediction of the long -te rm effects of the ground de position of the untre ate d and sinte red residue s w as att empted by applying the sugge sted models . It was shown that substantia l amount of time, 10 ye ars minim um, is ne e de d for the drop of the m e tals conce ntrations in the leachate to allowa ble lev e ls. The final stage of the proposed method contains the red uction smelting of the re sidues. A serie s of tests w as conducted in graphite crucibles in Tam mann furnace. The metal oxides re duction proce ss w as investi gated and the the rmod ynamic equilibrium of the hete rogen e ous actions betw e en liquid slag and me tal w as de te rmined in tempe ratures ranging from 1375 to 1600 oC. The therm od ynam ic equilibria functions conce rning the nickel, vanadium and iron oxides w ere exper ime ntally dete rmined. The e xpe rimental test heats yie lded final me tals recove ry rates of 85-98% for Ni and 78-95% for V , with simultaneous production of ne utralized slag suitable for deposition or othe r usage . The conditions that ma ximize the Ni and V re cove ries according to the expe rime ntal findi ngs we re:  the high tempe ratures  the use of graphite crucible  the Fe S i addi tions as re ductant In contrast to the dominating opinion, it w as shown that high rec ove ry rate s w e re achieved in high basicity rates of CaO/Si O 2>2, ensuring the re fractory lining of the furnace and the furthe r use of the produced slag. Alternatively, the direct re duction smelting of the physicochemic ally pretre ated re sidues was inve stigated. The finding that the small a dditions up to 10 % of boe hm itic type of bauxite improve the rec ove ries of nickel and in rate s highe r than 98% is ve ry important. The kinetics of the redu ction of iron and vanadium oxide s from the slag to the iron bath w ere also inve sti gate d and the corresponding constants and rate de te rmining ste ps we re de te rmined. viii A holisti c method of recycling the solid residue s of the oil-fire d stati ons is propose d The propose d me thod, in addition to high re cove ry rate s of the valuable alloying eleme nts containe d (nickel and vanadium) avoids the re sidue s treatment with expe nsive neutralization me thods. Mo reov e r, the ne utralization of these hazardous ma terials is achiev ed w ith substantial financial profit from the me tals re cove ry at the same time.