La méthode à privilégier pour améliorer dans les zéolithes la diffusion des réactifs, des intermédiaires réactionnels et des produits est de raccourcir la longueur du chemin diffusionnel, c'est-à-dire de diminuer la taille des cristaux. La croissance des cristallites est fonction de la composition du gel de synthèse, du temps de cristallisation, de la température, etc. La maîtrise de cette croissance permet d'obtenir un large éventail de taille pouvant aller de plusieurs micromètres à seulement quelques dizaines de nanomètres. Dorénavant, il est possible de limiter le chemin diffusionnel à seulement 3 mailles élémentaires en inhibant lors de la synthèse hydrothermale la croissance des cristaux dans une direction privilégiée. Pour cela l'utilisation d'agent structurant organique très particulier de type géminé s'avère indispensable et donne dans le cas de la zéolithe de type *BEA un matériau hiérarchisé avec des cristaux zéolithiques de 4 nm d'épaisseur séparés par des mésopores structurés et réguliers. La morphologie de ce matériau ressemble à une éponge de mer.<br>Deux réactions modèles, hydroisomérisation du n-héxadécane et transformation de l'éthanol en hydrocarbures, démontrent que la diffusion des réactifs et des produits sont optimisées dans les nanoéponges de bêta. La stabilité et la sélectivité du catalyseur se trouvent alors améliorées au détriment, étonnamment, de l'activité. Cela vient du fait que l'extrême diminution de l'épaisseur des cristallites conduit à une augmentation du nombre d'aluminium en bouche de pores qui sont, bien que très accessibles, incapables de catalyser les réactions d'isomérisation et de craquage. Les aluminium proche de la surface externe, contrairement à ceux situés au cœur du cristal ne bénéficient pas des effets longues distances ce qui les rend moins forts. / The method to ameliorate the diffusion of reactants, reaction intermediates, and products inside the zeolite is by shortening the diffusion path length, i.e., crystals size. The growth of the crystals is a function of gel composition synthesis, crystallization time, temperature, etc. The mastering of this growth allows to obtain a wide range of the size which ranges from several micrometers to a few tens of nanometers. It is possible now to limit the diffusion path to only three unit cells by inhibiting the crystals' growth in one direction during the hydrothermal synthesis. For that, the use of a peculiar organic surfactant geminate is indispensable, it gives a hierarchical material with zeolitic crystals of 4 nm thickness separated by structured and regular mesopores in the case of *BEA type zeolite. The morphology of this material resembles a sea sponge.<br>Two reaction models, n-hexadecane hydroisomerization and ethanol transformation to hydrocarbons, demonstrate that the reactants and the products diffusion was optimized in the beta nanosponges. Surprisingly the catalyst stability and selectivity were improved instead of activity. In fact this is due to the extreme reducing of the zeolite crystals’ thickness that leads to increase the aluminum number in the pore mouth, which although very accessible, but incapable to catalyze the isomerization and cracking reactions. The aluminums near the external surface, in contrary to those in the crystal heart, do not benefit from the long distance effects, which makes them weaker.

Brief experimental analysis (BEA) is a well-documented analysis strategy that rapidly manipulates instructional variables to identify the most effective intervention to support a student’s academic needs. However, consensus on how BEA data should be evaluated is not evident in published BEA articles. This study investigated the agreement between evaluation methods (i.e., visual analysis, no assumptions effect size, percentage of nonoverlapping data, nonoverlap of all pairs) used in BEA. Overall, the measures of effect size resulted in a higher percentage of positive agreement with other measures of effect size, in comparison to visual analysis paired with effect size measures. Use of effect size measures also resulted in less equivalency between intervention outcomes within a BEA. These data suggest that using a measure of effect size can be a beneficial component to visual analysis; however, each measure of effect size has its own strengths and limitations and should be used cautiously when interpreting results of a BEA.

Zugl.: Paderborn, Univ., Diss., 2005 u.d.T.: Recker, Dorothee: Auf dem Weg zum christlich-jüdischen Gespräch

In this diploma thesis, I focus on the application integration. Main goal of this thesis is comparison of integration platforms of the biggest vendors on the market, there are products of companies Microsoft, IBM, Oracle and SAP. I compare these products according criteria, which I had chosen. I use mainly own experiences with the products to achieve a goal. These products I compare with respect to general, technological and possibility of using point of view. My work can be as a source for decision, which of the integration platforms is optimal to use. Then I describe one of them - Microsoft Biztalk Server with simple example. The next goal of this work is to summarize the theory of application integration, where I describe the possibilities of integration's application from the simplest till the most complicated. The next goal of this work is making a methodology in Biztalk Server, which will contain concrete solutions and techniques in different situations. This methodology can help developers and analysts to make better proposals, more convenient solutions and beware of needless problems.

No description available.

No description available.

[ES] El aumento constante en la demanda de combustibles sumado a la crisis energética actual derivada de una escasez global de combustibles, y agravada por la suma de consecuencias de la pandemia COVID-19, la guerra de Ucrania y la crisis del gas, ha provocado una creciente búsqueda de nuevas alternativas para la obtención de combustibles. En este contexto, las refinerías se enfrentan al reto tanto de satisfacer la demanda de combustibles líquidos, como de cumplir con los requerimientos de calidad y medioambientales, cada vez más estrictos. El proceso de oligomerización de olefinas ligeras representa una ruta catalítica de gran interés para la obtención de productos de composición y calidad adecuadas para su posterior incorporación a los "pools" de gasolina, combustible de aviación y de diésel. Además de su versatilidad hacia la producción de un producto u otro en función de las condiciones de reacción y del tipo de catalizador empleado, permite el aprovechamiento de corrientes excedentes de refinería o procedentes de fuentes renovables ricas en olefinas. En este proceso los catalizadores ácidos, y entre ellos las zeolitas, han demostrado ser los más adecuados para la obtención de destilados medios de alta calidad. Sin embargo, los catalizadores basados en zeolitas presentan problemas difusionales que provocan su rápida desactivación. Por todo ello, la presente tesis se ha centrado en la mejora del proceso de oligomerización de penteno mediante el empleo de zeolitas nanocristalinas como catalizadores, con el fin de minimizar estas restricciones difusionales y de aumentar su tiempo de vida útil. Para la primera parte de la tesis se ha seleccionado la zeolita de poro grande beta (BEA) como catalizador de oligomerización y se ha preparado una serie de betas nanocristalinas con diferentes relaciones Si/Al en medio fluoruro y en medio OH. Se ha estudiado el efecto de la reducción del su tamaño de cristal y de la densidad de centros ácidos Brönsted en su comportamiento catalítico, y se ha caracterizado los catalizadores desactivados para estudiar el tipo de especies carbonosas formadas, responsables de la pérdida de actividad, y su posible regeneración. La segunda parte de la tesis se centra en el estudio del comportamiento catalítico de la zeolita multiporo ferrierita (FER). Así pues, se ha sintetizado una serie de zeolitas ferrieritas nanocristalinas con distintos tamaños de cristal y propiedades texturales y ácidas y se han evaluado como catalizadores en la oligomerización de penteno. La mejor de las nanoferrieritas, según los resultados obtenidos en oligomerización, se ha estudiado como catalizador en la isomerización de butenos a isobuteno, proceso que usa ferrierita a escala comercial. Su comportamiento catalítico se ha comparado con el de una ferrierita comercial, una ferrierita jerarquizada, una ITQ-6 deslaminada y una nanoferrierita parcialmente calcinada. Con esta última se ha estudiado el papel del coque en la mejora de la selectividad a isobuteno con el tiempo de reacción. Los resultados obtenidos en la reacción de oligomerización indican que la reducción en el tamaño de cristal de catalizadores basados en zeolitas es determinante para aumentar el tiempo de vida del catalizador. En el caso de las betas se ha visto que, incluso en el rango de los nanocristales, disminuir las dimensiones de 30-40 nm a 10-15 nm supone una mejora muy importante. En el caso de las ferrieritas se ha demostrado que es imprescindible que la reducción del cristal sea en la dirección en la que circulan los canales de 10 MR, que son los que participan en la reacción. En cuanto a la reacción de isomerización de buteno se ha conseguido aumentar la selectividad a isobuteno a valores superiores al 87 %, desde tiempos iniciales de reacción, para conversiones de buteno del 49 %, constantes durante al menos 50 h, mediante el empleo de una nanoferrierita parcialmente calcinada, en la que solo están presentes los centros activos en los canales de 10 MR. / [CA] L'augment constant en la demanda de combustibles sumat a la crisi energètica actual derivada d'una escassetat global de combustibles i agreujada per la suma de conseqüències de la pandèmia COVID-19, la guerra d'Ucraïna i la crisi del gas, ha provocat una recerca creixent de noves alternatives per obtindre combustibles. En aquest context, les refineries s'enfronten al repte tant de satisfer la demanda de combustibles líquids com de complir amb els requeriments de qualitat i mediambientals cada cop més estrictes. El procés d'oligomerització d'olefines lleugeres representa una ruta catalítica de gran interès per a l'obtenció de productes de composició i qualitat adequades per incorporar-los posteriorment als "pools" de gasolina, de combustible d'aviació i de dièsel. A més de la seua versatilitat cap a la producció d'un producte o altre en funció de les condicions de reacció i del tipus de catalitzador emprat, permet aprofitar corrents excedents de refineria o procedents de fonts renovables riques en olefines. En aquest procés, els catalitzadors àcids, i entre ells les zeolites, han demostrat ser els més adequats per a l'obtenció de destil·lats mitjans d'alta qualitat. Tot i això, els catalitzadors basats en zeolites presenten problemes difusionals que provoquen la seua ràpida desactivació. Per tot això, aquesta tesi s'ha centrat en la millora del procés d'oligomerització de pentè mitjançant l'ús de zeolites nanocristal·lines com a catalitzadors, per tal de minimitzar aquestes restriccions difusionals i augmentar-ne el temps de vida útil. Per a la primera part de la tesi s'ha seleccionat la zeolita de porus gran beta (BEA) com a catalitzador d'oligomerització i s'ha preparat una sèrie de betes nanocristalines amb diferents relacions Si/Al en medi fluorur i en medi OH. S'ha estudiat l'efecte de la reducció de la grandària de cristall i de la densitat de centres àcids Brönsted en el seu comportament catalític, i s'han caracteritzat els catalitzadors desactivats per estudiar el tipus d'espècies carbonoses formades, responsables de la pèrdua d'activitat, i la seua possible regeneració. La segona part de la tesi es centra a l'estudi del comportament catalític de la zeolita multiporus ferrierita (FER). Així, s'han sintetitzat una sèrie de ferrierites nanocristal·lines amb diferents grandàries de cristall i propietats texturals i àcides. D'una banda, s'han avaluat com a catalitzadors per a l'oligomerització del pente. D'altra banda, la millor nanoferrierita segons els resultats obtinguts en oligomerització s'ha estudiat com a catalitzador per a la isomerització estructural de butens a isobutè, ja que la ferrierita s'utilitza com a catalitzador al procés industrial d'isomerització. El seu comportament catalític s'ha comparat amb el d'una ferrierita comercial, una ferrierita jeràrquica, una ITQ-6 delaminada i una nanoferrierita parcialment calcinada. Aquest últim ha estat utilitzat per estudiar el paper que juga el coc en la millora de la selectivitat d'isobutè amb el temps en corrent. Els resultats obtinguts en la reacció d'oligomerització indiquen que la reducció en la grandària de cristall de catalitzadors basats en zeolites és determinant per augmentar el temps de vida del catalitzador. En el cas de les betes s'ha vist que, fins i tot en el rang dels nanocristalls, disminuir les dimensions de 30-40 nm a 10-15 nm suposa una millora molt important. En el cas de les ferrietes s'ha demostrat que és imprescindible que la reducció del vidre siga en la direcció on circulen els canals de 10 MR, que són els que participen a la reacció. Pel que fa a la reacció d'isomerització de butè, s'ha aconseguit augmentar la selectivitat a isobutè a valors superiors al 87 %, des de temps inicials de reacció, per a conversions de butè de 49 %, constants durant almenys 50 h mitjançant l'ús de una nanoferrierita parcialment calcinada, on només hi són presents els centres actius als canals de 10 MR. / [EN] The constant increase in the demands of fuels, together with the present energy crisis derived from the global fuels' shortage caused by the COVID-19 pandemic, the Ukraine war and the gas crisis, has forced refiners to search for alternative routes for fuels production. Thus, refineries face the challenge of satisfying both, the demand for liquid fuels and the quality and environmental requirements, increasingly strict. Light olefin oligomerization represents a catalytic route of high interest for the production of liquid fuels with the desired composition and quality to be incorporated to the gasoline, jet fuel or diesel pools. Besides its versatility in terms of product selectivity as a function of reaction conditions and catalyst employed, it allows the revalorization of low value refinery or bio-derived olefin-rich streams. Acid catalyst and, in particular, zeolites have proved to be the most suitable catalysts for the production of high quality distillates. However, zeolite-based catalysts present diffusional problems that lead to fast deactivation rates. Taking all this into account, the present thesis focuses on the improvement of the pentene oligomerization process by means of using nanocrystalline zeolites as catalysts, aiming to minimize diffusional restrictions and to increase their catalyst life. In the first part of the thesis, the large pore beta zeolite (BEA) has been selected as oligomerization catalyst, and a series of nanocristalline betas with different Si/Al ratios have been prepared in fluoride and in OH media. The influence of crystal size reduction and Brönsted acid site density on their catalytic performance has been studied and the spent catalysts have been characterized in order to study the type of carbon species formed, responsible for the activity loss, and their possible regeneration. The second part of the thesis focuses on the study of the catalytic performance of the multipore ferrierite. Thus, a series of nanocrystalline zeolites has been synthesized with different crystal sizes and textural and acidic properties. On the one hand, they have been evaluated as catalysts for the pentene oligomerization. On the other, the best nanoferrierite according to the results obtained in oligomerization has been studied as catalyst for the structural isomerization of butenes to isobutene, as ferrierita is used as catalyst in the industrial isomerization process. Its catalytic performance has been compared with that of a commercial ferrierita, a hierarchical ferrierite, a delaminated ITQ-6 and a nanoferrierite partially calcined. The latter has been used to study the role played by coke in the improvement with time on stream of the isobutene selectivity. The results obtained in the oligomerization reaction indicate that crystal size reduction in zeolite-based catalysts is key for increasing the catalysts life. In case of the beta zeolites it has been proved that decreasing the nanocrystals size from 30-40 nm to 10-15 nm leads to a very significant improvement in catalyst life. In the case of ferrierites it has been demonstrated that it is essential to reduce the crystal size in the direction parallel to the 10 MR channels, which are those involved in the oligomerization reaction. When used as catalysts for butenes isomerization, the use of partially calcined nanoferrierites, with active sites present only in the 10 MR, has led to isobutene selectivities above 87 % since very short times on stream, for butene conversion of 49 %, constant for at least 50 h. / Díaz Rey, MDR. (2023). Optimización de procesos de revalorización de olefinas ligeras mediante el empleo de catalizadores basados en zeolitas nanocristalinas [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/192869

Made available in DSpace on 2016-06-02T19:55:40Z (GMT). No. of bitstreams: 1 6262.pdf: 12922381 bytes, checksum: d9847d4190f445fab3aa2cb28bd467a1 (MD5) Previous issue date: 2014-08-22 / Universidade Federal de Minas Gerais / The use of zeolites in basic catalysis is small, especially when compared to the numerous applications of material in their acid form. Inside this context, are even smaller the number of studies on the use of as-synthesized zeolites as basic catalysts. Zeolites are crystalline hydrated aluminosilicates that have a pores size well-defined. Many of zeolite structures need organic compounds to be synthesized, these compounds are called structure directing agents. Zeolites containing organic cations (as-synthesized) have basic properties and can be used as catalysts in reactions that require this type of catalytic site. In this work were investigated three zeolites structures widely studied in the literature, BEA, MFI and MTW. Zeolites were synthesized with different compositions (ratio Si/Al) in the reaction mixture. Addition to the conventional synthesis were performed modifications using an organosilane (TPOAC - trimethoxysilyl-propyl-octadecylammonio chloride) in the synthesis of structures MFI and MTW. Were obtained, for the three structures, samples with different Si/Al ratios, some of them containing organosilane. The samples were characterized and used as catalysts in the Knoevenagel condensation. For all samples the increase of the Si/Al ratio increased the number of species [&#8801;Si O ][TEA+]. The characterization and catalytic conversion show that for BEA zeolite only one portion of the species [&#8801;Si O ][TEA+] were available for the reaction. The samples modified with organosilane (TPOAC) were the most active, especially with MTW structure. This increased activity is related to the modification that the organosilane promoted on the surface of the particles. The addition of organosilane favored the increase of the Si/Al ratio on the surface and this may be related to better conversion results. In this work, we propose new efficient catalysts, with zeolitic structure, for reactions involving basic sites. / O uso de zeólitas em catálise básica ainda é muito pequeno, principalmente quando comparado às inúmeras aplicações de material em sua forma ácida. Dentro desse contexto, é menor ainda o número de estudos sobre a utilização de zeólitas tal como sintetizadas como catalisadores básicos. Zeólitas são aluminosilicatos hidratados cristalinos que possuem um tamanho de poros muito bem definidos. Muitas das estruturas zeolíticas precisam de compostos orgânicos para serem sintetizadas, esses compostos são chamados de direcionadores de estrutura. Zeólitas contendo cátions orgânicos (tal como sintetizadas) possuem propriedades básicas e podem ser usadas como catalisadores em reação que necessitam esse tipo de sítio catalítico. Nesse trabalho foram investigadas 3 estruturas zeólitas bastante estudadas na literatura, BEA, MFI e MTW. As zeólitas foram sintetizadas com diferentes composições (razão Si/Al) na mistura reacional. Além da síntese convencional foram realizadas também modificações usando um organossilano (TPOAC Cloreto de Trimetoxisilil-propil-octadecilamônio) na síntese das estruturas MFI e MTW. Foram obtidas, para as 3 estruturas, amostras com diferentes razões Si/Al, algumas delas contendo organossilano. As amostras foram caraterizadas e usadas como catalisadores na reação de condensação de Knoevenagel. Para todas as amostras o aumento da razão Si/Al levou ao aumento da quantidade das espécies [&#8801;Si O ][TEA+]. As caracterizações e os resultados de conversão catalítica mostram que para a zeólita BEA apenas parte das espécies [&#8801;Si O ][TEA+] estavam na superfície disponíveis para a reação. As amostras modificadas com organossilano (TPOAC) foram as mais ativas, principalmente as com estrutura MTW. Essa maior atividade está relacionada a modificação que o organossilano promoveu na superfície das partículas. A adição de organossilano favoreceu o aumento da razão Si/Al na superfície e isso pode estar relacionado aos melhores resultados de conversão. Nesse trabalho, propomos novos catalisadores eficientes, a base de zeólitas, para reações que envolvam sítios básicos.

Based on the design decision making process from an architect’s point of view, a related literature review, theoretical analyses, and inductive inferences, this thesis proposes a new interpretation of high-performance building (HPB), translates/maps criteria issues related to building environmental assessment (BEA) tools for key design decision making elements, and identifies sources of inspiration for HPB designs. This thesis intends to propose an integrated conceptual model for the design of HPBs to provide direct knowledge-based decision making support to architects in the early design phase. Studies on key design decision making elements, sources of inspiration, and building information modeling are integrated into this genesis of conceptual design. The concept of the HPB proposed in this thesis emphasizes comprehensive sustainable building performance in environmental, economic, and socio-cultural aspects. The concept takes the view that HPBs should be aesthetically attractive, socio-culturally adapted, safe, healthy, and comfortable, and should operate at a high level of environmental, resource, and economic efficiency throughout their life cycle. This thesis discusses the topics of the necessity, benefits, and design principles of HPBs. An analysis of the characteristics of BEA tools and HPB design decision making revealed their relationship: the consequence of goals and the mismatch of practices. BEA tools provide the basic information (such as framework, content, evaluation methods, and processes) related to decision making to promote a holistic HPB design at a practical level. However, given the mismatch of practices between BEA tools and HPB design decision making, most such tools are still used for testing and verifying the design results and do not consider the design decision making process. Existing BEA tools primarily guide or indirectly affect the design work but, in practice, play a limited role in directly helping architects make early decisions regarding HPB design. First, for a detailed comparison, this thesis identified the common criteria issues for the three existing BEA tools: SBTool 2012 (maximum version), LEED NC-v3, and the Chinese Evaluation Standard for Green Building (ESGB). A total of 51 common/similar criteria issues were identified and such issues were found to be primarily allocated in the energy and resources, indoor environmental quality, environmental loads, and site areas. SBTool 2012 contains the widest range and most comprehensive criteria issues of building performance, whereas the LEED NC-v3 and ESGB frameworks poorly cover social- and economic-related issues. Second, this thesis separated the criteria into whether they relate to decision making factors or building performance factors. Third, this thesis mapped HPB criteria issues into HPB design decision making elements. This thesis establishes a framework for key design decision elements for Chinese residential buildings by selecting a residential building type in China as a case study for the mapping approach application. The optimum criteria issues for Chinese residential buildings contain 10 primary criteria issues and 35 sub-criteria issues that cover aspects within the entire sustainable performance range and that correspond to key design decision making elements in this framework. This thesis also proposes two fundamental support approaches to creative design for HPBs: rational technical support and irrational divergent inspirational support. Based on practical design examples, three major types of irrational sources of inspiration in an architect’s design for HPBs have been identified: previous empirics, nature objects and phenomena, and advanced science and technologies. Finally, a new integrated conceptual model to support an architect’s early design decisions is established based on the BIM platform. The model contains two main aspects of the work: an initial building information model and an optimal building information model for HPBs during the early design stage. This conceptual model is presented as a generic approach that can be customized for different designers and project conditions. The model can also be used as a framework for providing knowledge-based creative support for decision making related to HPB design. In summary, this thesis intends to provide both a theoretical base and feasible measures for better HPB design and references for developing design decision making support tools for architects to use during the early HPB design process. / <p>QC 20131115</p>

Expression globalisante des moyens d’action du secteur privé au service du secteur public, le partenariat public-privé pourrait être appréhendé comme révélant l’effritement des catégories notionnelles des contrats de commande publique. Cependant, le partenariat public-privé n’a pas remis en cause l’unité de la matière. Au contraire, les instruments juridiques du P.P.P. la renforcent. Cette analyse se vérifie aussi bien en France qu’en Italie et cette étude se propose d’analyser la signification juridique du phénomène dans ces deux pays. Les évolutions induites par la notion s’inscrivent dans cette logique. La démarche comparatiste utilisée permet alors de comprendre les tenants et les aboutissants de cette évolution et s’inscrit dès lors comme une contribution à la théorie générale des contrats publics. / Holistic expression as a means of action by the private sector to further the public sector, the publicprivate partnership could be perceived as revealing the erosion of the notional categories of public procurment contracts. However, the public-private partnership has not called into question the subject unity. In fact, on the contrary, the legal instruments of the PPP strentgthen it. This analysis can be verified in France as well as in Italy and the present study offers to analyse the legal signification of the phenomenon in both countries. The development induced by this notion confirms this trend. The comparative approach enables to understand the whys and wherfores of the development and formspart of the general theory of public contracts. / Espressione globalizzata dei mezzi d’azione del settore privato al servizio del settore pubblico, il partenariato pubblico-privato potrebbe essere visto come rivela la dislocazione delle categorie del diritto dei contratti pubblici. Tuttavia, il partenariato pubblico-privato essa non pregiudica sulll'unitàdella disciplina. Invece, gli strumenti giuridici del P.P.P la rafforza. Questa analisi è confermata in Francia e in Italia ed lo studio permette di analizzare l'importanza giuridica del fenomeno in i due paesi. L'approccio comparativo utilizzato permette di capire questa evoluzione e può essere percepitocome un contributo alla teoria giuridica dei contratti pubblici.