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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
61

Ethylene to Liquid Hydrocarbons by Heterogeneously Catalyzed Oligomerization on ZSM-5

Halldén, Gustav January 2022 (has links)
The aim is to produce aliphatic liquid hydrocarbons using heterogeneous ethylene oligomerization. Thiscould potentially produce renewable synthetic fuels. Heterogeneous catalysis has some advantages overhomogeneous catalysis regarding some sustainability aspects. To achieve this, a setup was built using a heatedfixed bed reactor with an in-situ has chromatography to study conversion and gaseous products, and ex-situGC as well as NMR for analyzing liquid products. Ethylene was oligomerized on a commercial ZSM-5 zeoliteunder varying temperature conditions and feed gas dilution with hydrogen or helium. The gas and liquidproducts were analyzed and evaluated. Additionally, the ZSM-5 was studied at different silica to alumina ratios. The thesis discusses how conversion, liquid yield and selectivity of gas products using GC together withanalysis of liquid products using H-NMR can be used as a simple and quick evaluation. The liquid product isevaluated by the distribution of olefinic and aromatic hydrocarbon species using the hydrogen signal area inthe characteristic chemical shifts of olefinic and aromatic hydrogen. At 250-400oC, 6 bar of ethylene, with andwithout feed dilution, and WHSV of 204 h-1, conversion was consistently above 95% for the diluted 400oCruns. Though the liquid yield fell to around 6%, compared to the best yield at 18% for the pure 300oC run.Diluting the feed had a positive effect on increasing olefinic hydrogen signal while decreasing aromatichydrogen signal. The difference between diluting with H2 or helium had a surprisingly small effect. Decreasingthe Si/Al ratio had no significant effect on performance, while increasing the Si/Al ratio made the zeolite loseits catalytic ability. With a pure ethylene feed the lowest aromatic hydrogen signal was found at 350oC, whilethe olefinic signal did not vary too much with temperature. With diluted feed the higher temperature did leadto a lower olefinic hydrogen signal and higher aromatic hydrogen signal.
62

Avalia??o da s?ntese e caracteriza??o de ze?lita ZSM-5 ausente de direcionador org?nico estrutural

Caldeira, Vin?cius Patr?cio da Silva 25 February 2011 (has links)
Made available in DSpace on 2014-12-17T15:41:53Z (GMT). No. of bitstreams: 1 ViniciusPSC_DISSERT.pdf: 2657914 bytes, checksum: beb97c8aaf506ef6b97930de865d3dd2 (MD5) Previous issue date: 2011-02-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The catalytic processes play a vital role in the worldwide economy, a business that handles about US$ 13 billion per year because the value of products depends on the catalytic processes, including petroleum products, chemicals, pharmaceuticals, synthetic rubbers and plastics, among others. The zeolite ZSM-5 is used as catalyst for various reactions in the area petrochemical, petroleum refining and fine chemicals, especially the reactions of cracking, isomerization, alkylation, aromatization of olefins, among others. Many researchers have studied the hydrothermal synthesis of zeolite ZSM-5 free template and they obtained satisfactory results, so this study aims to evaluate the hydrothermal synthesis and the physicochemical properties of ZSM-5 with the presence and absence of template compared with commercial ZSM-5. The methods for hydrothermal synthesis of zeolite ZSM-5 are of scientific knowledge, providing the chemical composition required for the formation of zeolitic structure in the presence and absence of template. Samples of both zeolites ZSM-5 in protonic form were obtained by heat treatment and ion exchange, according to procedures reported in the literature. The sample of commercial ZSM-5 was acquired by the company Sentex Industrial Ltda. All samples were characterized by XRD, SEM, FTIR, TG / DTG / DSC, N2 adsorption and desorption and study of acidity by thermo-desorption of probe molecule (n-butylamine), in order to understand their physicochemical properties. The efficiency of the methods applied in this work and reported in the literature has been proved by well-defined structure of ZSM-5. According as the evaluation of physicochemical properties, zeolite ZSM-5 free template becomes promising for application in the refining processes or use as catalytic support, since its synthesis reduces environmental impacts and production costs / Os processos catal?ticos desempenham um papel vital na economia mundial, um neg?cio que movimenta aproximadamente US$13 bilh?es por ano, pois o valor dos produtos depende dos processos catal?ticos, incluindo os produtos petrol?feros, qu?micos, farmac?uticos, borrachas sint?ticas e pl?sticos, entre outros. A ze?lita ZSM-5 ? utilizada como catalisador em rea??es nas ?reas petroqu?mica, petrol?fera e qu?mica fina, destacando-se as rea??es de craqueamento, isomeriza??o, alquila??o, aromatiza??o de olefinas, entre outras. Muitos pesquisadores t?m estudado a s?ntese hidrot?rmica da ze?lita ZSM-5 ausente de direcionador org?nico estrutural e obtiveram resultados satisfat?rios, assim, este estudo visa avaliar a s?ntese hidrot?rmica e as propriedades f?sico-qu?micas da ZSM-5 com a presen?a e aus?ncia de direcionador org?nico estrutural, em compara??o com ZSM-5 comercial. Os m?todos para a s?ntese hidrot?rmica da ze?lita ZSM-5 s?o de conhecimento cient?fico, fornecendo a composi??o qu?mica necess?ria para a forma??o da estrutura zeol?tica em presen?a e aus?ncia de direcionador org?nico estrutural. As amostras de ambas as ze?litas ZSM-5 na forma prot?nica foram obtidas atrav?s de tratamentos t?rmicos e troca i?nica, de acordo com procedimentos relatados na literatura. A amostra de ZSM-5 comercial foi concedida pela empresa Sentex Industrial Ltda. Todas as amostras foram caracterizadas por DRX, MEV, FTIR, TG/DTG/DSC, Adsor??o e dessor??o de N2 e estudo da acidez por termodessor??o de mol?cula sonda (n-butilamina), a fim de compreender suas propriedades f?sico-qu?micas. A efici?ncia dos m?todos aplicados no presente trabalho e relatados na literatura foi comprovada pela estrutura bem definida da ze?lita ZSM-5. Conforme a avalia??o das propriedades f?sico-qu?micas, a ze?lita ZSM-5 ausente de direcionador org?nico torna-se promissora para aplica??o em processos de refino ou utiliza??o como suporte catal?tico, visto que, sua s?ntese reduz os impactos ambientais e custos de produ??o
63

Untersuchungen an nickelhaltigen ZSM-5-Zeolith-Katalysatoren zur simultanen Stickoxidreduktion mit Propen / Investigations on nickel containing zeolites of type ZSM-5 for simultaneous reduction of nitric and nitrous oxides with propene

Räuchle, Konstantin 08 February 2006 (has links) (PDF)
Stickoxide (NOx) und Distickstoffoxid (N2O) entstehen bei der Verbrennung fossiler Brennstoffe in Gegenwart von Luft und gehören auf Grund ihrer toxischen bzw. klimaschädigenden Wirkung zu den Luftschadstoffen. In der Arbeit wird die simultane Reduktion von NOx und N2O an nickelbeladenen Zeolithen vom Typ H-ZSM-5 mit Propen als Reduktionsmittel untersucht. Die experimentellen Arbeiten wurden unter realitätsnahen Bedingungen mit einem Katalysatorbett durchgeführt. Der Einfluss des Nickelgehalts und der Acidität des zeolithischen Trägermaterials auf Umsatz und Selektivität der Reduktion werden diskutiert. Ausgehend von den gewonnenen Ergebnissen wird ein wahrscheinlicher Reduktionsmechanismus vorgeschlagen. / Nitric and nitrous oxides (NOx, N2O) are part of toxic and climate damaging airborne pollutants and will be produced by combustion of fossil fuels in present of air. In this work the simultaneous reduction of NOx and N2O with propene has been investigated using nickel impregnated zeolites of type H-ZSM-5 as catalytic active material. The experiments have been done using one catalyst bed and a synthetic gas mixture according to real existing environment conditions. The influence of nickel content as well as acidity of the support material on conversion and selectivity have been discussed. Using the experimental results a possible reaction mechanism has been submitted.
64

Metal nanoparticles encapsulated in membrane-like zeolite single crystals : application to selective catalysis / Nanoparticules métalliques encapsulées dans des nanoboites zéolithiques : applications à des réactions de catalyse sélective

Li, Shiwen 05 May 2015 (has links)
Les matériaux « coeur-coquille » composés d’une nanoparticule métallique encapsulée à l'intérieur de coquilles inorganiques (oxydes, carbone …) attirent de plus en plus l'attention par leurs propriétés particulières, en particulier dans le domaine de la catalyse. Les particules métalliques sont protégées par la coquille, qui empêche entre autres le frittage et la croissance des particules à haute température. Cependant, les coquilles sont généralement méso à macroporeuses et elles ne peuvent pas jouer le rôle de tamis moléculaire pour les molécules de taille nanométrique. En revanche, les zéolithes sont des solides cristallins microporeux dont les pores bien définis permettent une forte discrimination des réactifs basée sur la taille, la forme ou leur coefficient de diffusion. L’objectif de cette thèse visait à la synthèse de catalyseurs de type coeur-coquille dans lesquels la coquille est une zéolite microporeuse de structure MFI (silicalite-1 et ZSM-5), le coeur étant soit une particule de métal noble (Au, Ag, Pt, Pd), soit des alliages de ces différents métaux, soit enfin un métal de transition (Co, Ni, Cu). Ces catalyseurs ont été appliqués dans des réactions d'hydrogénation sélective (aromatiques substitués) et l'oxydation sélective de CO en présence d'hydrocarbures. Nous avons ainsi montré que la coquille zéolithique, tout en protégeant les particules du frittage, modifie la sélectivité des réactions en interdisant aux réactifs volumineux d’atteindre les sites catalytiques / Nanostructured yolk-shell materials, which consist of metal nanoparticle cores encapsulated inside hollow shells, attract more and more attention in material science and catalyst applications during the last two decades. Metal particles are usually highly mono-dispersed in size and isolated from each other by the shell, which prevents growth by sintering at high temperature. Because they are generally made of meso/macroporous oxides or amorphous carbon, shells cannot carry out molecular sieve-type separation of molecules at the nanometric scale. The aim of the present thesis was to synthesize yolk-shell catalyst with microporous zeolite shells (silicalite-1 and ZSM-5), containing noble (Au, Pt, Pd) transition (Co, Ni, Cu) and alloy metal nanoparticles. Zeolites are crystalline microporous solids with well-defined pores capable of discriminating nanometric reactants on the basis of size, shape and diffusion rate. Zeolite-based yolk-shell catalysts have been applied in selective hydrogenation (toluene and mesitylene) and oxidation (CO) reactions in the presence of hydrocarbons. Zeolite shells not only plaid a key role as membranes, thus changing selectivities as compared to conventional supported catalysts, but they also protected metal nanoparticles from sintering under reaction conditions
65

Untersuchungen an nickelhaltigen ZSM-5-Zeolith-Katalysatoren zur simultanen Stickoxidreduktion mit Propen

Räuchle, Konstantin 19 September 2005 (has links)
Stickoxide (NOx) und Distickstoffoxid (N2O) entstehen bei der Verbrennung fossiler Brennstoffe in Gegenwart von Luft und gehören auf Grund ihrer toxischen bzw. klimaschädigenden Wirkung zu den Luftschadstoffen. In der Arbeit wird die simultane Reduktion von NOx und N2O an nickelbeladenen Zeolithen vom Typ H-ZSM-5 mit Propen als Reduktionsmittel untersucht. Die experimentellen Arbeiten wurden unter realitätsnahen Bedingungen mit einem Katalysatorbett durchgeführt. Der Einfluss des Nickelgehalts und der Acidität des zeolithischen Trägermaterials auf Umsatz und Selektivität der Reduktion werden diskutiert. Ausgehend von den gewonnenen Ergebnissen wird ein wahrscheinlicher Reduktionsmechanismus vorgeschlagen. / Nitric and nitrous oxides (NOx, N2O) are part of toxic and climate damaging airborne pollutants and will be produced by combustion of fossil fuels in present of air. In this work the simultaneous reduction of NOx and N2O with propene has been investigated using nickel impregnated zeolites of type H-ZSM-5 as catalytic active material. The experiments have been done using one catalyst bed and a synthetic gas mixture according to real existing environment conditions. The influence of nickel content as well as acidity of the support material on conversion and selectivity have been discussed. Using the experimental results a possible reaction mechanism has been submitted.
66

S?ntese e caracteriza??o de materiais nanoporosos para pir?lise catal?tica de ?leos pesados

Costa, Maria Jos? Fonseca 22 December 2008 (has links)
Made available in DSpace on 2014-12-17T15:41:45Z (GMT). No. of bitstreams: 1 MariaJFCpdf.pdf: 4931245 bytes, checksum: 45a7ea893d17f478c73adf56787579aa (MD5) Previous issue date: 2008-12-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The present work reports the study of nanoporous structures, aiming at their use in research directed to the current demand of the petroleum industry to value heavy oil. Initially, two ways were chosen for the synthesis of porous structures from the molecular sieves of type Si-MCM-41. In the first way, the structure MCM-41 is precursory for heteroatom substitutes of silicon, generating catalyst of the type Al-MCM-41 from two different methods of incorporation of the metal. This variation of the incorporation method of Aluminum in the structure of Si-MCM-41 was carried out through the conventional procedure, where the aluminum source was incorporated to the gel of synthesis, and the procedure post-synthesis, where the Aluminum source was incorporated in catalyst after the synthesis of Si-MCM-41. In the second way, the MCM-41 acts as a support for growth of nanocrystals of zeolite embedded in their mesoporous, resulting in hybrid MCM-41/ZSM-5 catalyst. A comparative analysis was carried through characterizations by XRD, FTIR, measures of acidity through n-butylamine adsorption for TGA, SEM-XRF and N2 adsorption. Also crystalline aluminosilicate with zeolitic structure MFI of type ZSM-5 was synthesized without using organic templates. Methodologies to the preparation of these materials are related by literature using conventionally reactants that supply oxides of necessary silicon and aluminum, as well as a template agent, and in some cases co-template. The search for new routes of preparation for the ZSM-5 aimed at, above all, the optimization of the same as for the time and the temperature of synthesis, and mainly the elimination of the use of organic templates, that are material of high cost and generally very toxic. The current study is based on the use of the H2O and Na+ cations playing the role of structural template and charge compensation in the structure. Characterizations by XRD, FTIR, SEM-XRF and N2 adsorption were also conducted for this material in order to compare the samples of ZSM-5 synthesized in the absence of template and those used industrially and synthesized using structuring / O presente trabalho relata o estudo de estruturas nanoporosas, visando o uso em pesquisas que atendam a atual demanda da ind?stria do petr?leo, de valorizar ?leos pesados. Inicialmente, optou-se por duas vertentes para a s?ntese de estruturas porosas a partir da peneira molecular do tipo Si-MCM-41. Na primeira vertente, a estrutura MCM-41 ? precursora para hetero?tomos substituintes do sil?cio, gerando catalisadores do tipo Al-MCM-41 a partir de dois diferentes m?todos de incorpora??o do metal. Essa varia??o do m?todo de incorpora??o do Alum?nio na estrutura do Si-MCM-41 se deu atrav?s do procedimento convencional, no qual a fonte de alum?nio foi incorporada ao gel de s?ntese e do procedimento p?s-s?ntese, no qual a fonte de Alum?nio foi incorporada ao catalisador ap?s a s?ntese do Si-MCM-41. Na segunda vertente, o MCM-41 age como suporte para o crescimento de nanocristais de ze?lita embutidos nos seus mesoporos, resultando no catalisador h?brido MCM-41/ZSM-5. Uma an?lise comparativa foi realizada atrav?s de caracteriza??es por XRD, FTIR, medidas de acidez atrav?s de dessor??o de n-butilamina por TGA, SEM-XRF e Adsor??o de N2. Tamb?m foi sintetizado um aluminossilicato cristalino com estrutura zeol?tica MFI do tipo ZSM-5, na aus?ncia total de direcionador org?nico. Metodologias relacionadas ? prepara??o desses materiais s?o relatadas pela literatura utilizando-se convencionalmente reagentes que forne?am os ?xidos de sil?cio e de alum?nio necess?rios, bem como um agente direcionador, e em alguns casos at? co-direcionadores. A busca por novas rotas de prepara??o para a ZSM-5 visou, sobretudo, a otimiza??o da mesma no que se refere ao tempo e ? temperatura de s?ntese, e principalmente a elimina??o do uso dos direcionadores org?nicos, que s?o materiais de alto custo e geralmente muito t?xicos. O atual estudo se baseia na utiliza??o da H2O e dos c?tions Na+ desempenhando o papel de direcionamento estrutural e compensa??o de cargas na estrutura. Caracteriza??es por XRD, FTIR, SEM-XRF e Adsor??o de N2 tamb?m foram realizadas para esse material, a fim de comparar as amostras de ZSM-5 sintetizadas na aus?ncia do direcionador e aquelas utilizadas industrialmente e sintetizadas utilizando estruturantes
67

Influence de la symétrie et de la taille de la molécule adsorbée sur le processus d'adsorption des composés éthyléniques sur une zéolithe de topologie MFI

Bernardet, Véronique 12 December 2005 (has links) (PDF)
Cette étude s'inscrit dans le cadre de la compréhension des isothermes à sous-marche observées durant l'adsorption, sur les zéolithes de type MFI, de certains composés organiques. Pour cela, le processus d'adsorption de l'éthylène et du tétraméthyléthylène a été étudié en premier lieu par gravimétrie et en second lieu par spectroscopie infrarouge in situ. Cette dernière technique permet de suivre simultanément les modifications de l'adsorbant et de l'adsorbat. L'analyse de ces données laisse supposer que la sous-marche dans l'isotherme d'adsorption peut être expliquée en tenant compte simultanément de la symétrie et de la taille de la molécule adsorbée. En plus des bandes infrarouge caractéristiques de l'adsorbant et de la phase adsorbée, une bande émergeante est mise en évidence. Elle peut être considérée comme une empreinte du processus d'adsorption.
68

Study Of Sorption Of Alcohols On High Silica Zsm-35

Babuccuoglu, Yurdaer 01 January 2007 (has links) (PDF)
This study investigated the equilibrium sorption capacities and rates of sorption of some alcohols on Na- and/or H- form of ZSM-35 at different temperatures by gravimetric method using an electrobalance. The alcohols studied were methanol, ethanol, propan-1-ol, propan-2-ol, n-butanol. The ZSM-35 sample used in sorption experiments resulted from a study for synthesis of high silica ZSM-35 zeolite. This ZSM-35 sample was called as NaZSM-35. The influence of ion-exchange on the sorption capacity and kinetics was investigated by converting NaZSM-35 into H-form by the ion exchange method. In this method, a sufficient amount of ZSM-35 sample (200-250 mg) was mixed with 25 ml of 1 N NH4Cl solution for 24 hours at room temperature. This procedure was repeated until no Na+ was detected by a Flame Photometer. After the ion exchange was completed , the sample was washed with deionized water, filtered, dried and recalcined for the removal of the ammonia and this sample was denoted as HZSM-35. The highest sorption capacity (cm3/g) was observed for methanol on HZSM-35 / 0.1656 cm3/g and the lowest sorption capacity was observed for propan-2-ol at NaZSM-35 / 0.003 cm3/g. Sorption of methanol and ethanol were very rapid. The sorption capacities of other three alcohols / propan-1-ol, propan-2-ol and n-butanol, were lower and they had slower rates of sorption. HZSM-35 had greater limiting sorption capacity than NaZSM-35 for propan-1-ol, propan-2-ol and n-butanol at all temperatures.
69

Síntese de membranas zeolíticas (ZSM-5/y-ALUMINA e ZSM-5/a-ALUMINA) por Pore-Plugging para permeação de gás N2. / Synthesis of zeolite membranes (ZSM-5 / y-ALUMINA and ZSM-5 / a-ALUMINA) by Pore-Plugging for N2 gas permeation

SCHEIBLER, Janaina Rafaella. 23 March 2018 (has links)
Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T18:44:54Z No. of bitstreams: 1 JANAINA RAFAELLA SCHEIBLER - DISSERTAÇÃO PPGEQ 2015..pdf: 2465420 bytes, checksum: cbecc726b67d3d76a334570b655735eb (MD5) / Made available in DSpace on 2018-03-23T18:44:54Z (GMT). No. of bitstreams: 1 JANAINA RAFAELLA SCHEIBLER - DISSERTAÇÃO PPGEQ 2015..pdf: 2465420 bytes, checksum: cbecc726b67d3d76a334570b655735eb (MD5) Previous issue date: 2015 / Entre as membranas inorgânicas microporosas, as membranas zeolíticas constituem uma tecnologia promissora, devido às suas potenciais aplicações normalmente na desidratação do álcool, separação de moléculas de gás, separação de isômeros ou em processos químicos, incluindo reações de esterificação. Sob este aspecto, torna-se imprescindível o estudo das rotas de preparação desses materiais, visando desenvolver produtos com qualidade e a baixo custo. Portanto, a inovação deste estudo se dá na síntese de membranas zeolíticas via método de síntese poreplugging visando a utilização das membranas inorgânicas para permeação gasosa de N2. Neste trabalho foram desenvolvidos os seguintes materiais: zeólita ZSM-5, membranas cerâmicas (γ-alumina e α-alumina) e as membranas zeolíticas (ZSM5/γ-alumina e ZSM-5/α-alumina). A zeólita ZSM-5 foi sintetizada por meio do método hidrotérmico. As membranas cerâmicas (γ-alumina e α-alumina) foram preparadas a partir da técnica de conformação de pós cerâmicos e posteriormente submetidas à sinterização a uma temperatura de 1000 ºC/1h e 1200 ºC/1h respectivamente. A preparação das membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina) foi realizada com base no método pore in plugging. As amostras foram caracterizadas a partir das técnicas de difração de raios X e Microscopia Eletrônica de Varredura. Os resultados experimentais permitem diversas conclusões acerca do desenvolvimento dos materiais: zeólita ZSM-5, membranas cerâmicas (γ-alumina e α-alumina) e membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina). A partir da difração de raios X, foi possível verificar que o método de síntese empregado, foi efetivo na obtenção da zeólita ZSM-5. O difratograma apresentou picos característicos de uma zeólita ZSM-5 quando comparada ao padrão. Os resultados obtidos por DRX para as membranas cerâmicas (γ-alumina e α-alumina) demonstraram a formação de picos característicos do óxido de alumínio, os materiais são cristalinos e puros. Para o método pore-plugging pode se dizer que é um método promissor, pois mostrou uma formação satisfatória da camada zeolítica no resultado do DRX de ambas as membranas zeolíticas (ZSM-5/γ-alumina e ZSM-5/α-alumina). / Among the microporous inorganic membranes, zeolite membranes are a promising technology due to their potential applications normally in alcohol dehydration, separation of gas molecules, separation of isomers or chemical processes, including esterification reactions. In this regard, it is essential to study the preparation of these materials routes in order to develop products with quality and low cost. Therefore, innovation of this study gives the synthesis of zeolite membranes via pore-plugging synthesis method aimed at the use of inorganic membranes for gas permeation N2. In this work the following materials were developed: ZSM-5 zeolite, ceramic membranes (γ-alumina and α-alumina) and zeolitic membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina). Zeolite ZSM-5 was synthesized by the hydrothermal method. Ceramic membranes (γ-alumina and α-alumina) were prepared from the ceramic powder forming technique, and subsequently subjected to a sintering temperature of 1000 °C/1h and 1200 °C/1h respectively. The preparation of zeolite membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina) was carried out based on the method in pore plugging. The samples were characterized from the techniques of X diffraction and scanning electron microscopy rays. The experimental results allow several conclusions about the development of materials: zeolite ZSM-5, ceramic membranes (γ-alumina and α-alumina) and zeolite membranes (ZSM-5/γ-alumina and ZSM-5/αalumina). From the X-ray diffraction, it found that the method of synthesis used was effective in obtaining the zeolite ZSM-5. The XRD pattern showed peaks characteristic of ZSM-5 compared to the standard. The results obtained by XRD ceramic membranes (γ-alumina and α-alumina) showed the formation of peaks characteristic of aluminum oxide, the materials are crystalline and pure. For the poreplugging method can be said to be a promising method because it showed a satisfactory formation of the zeolite layer on the result of XRD both zeolite membranes (ZSM-5/γ-alumina and ZSM-5/α-alumina).
70

Síntese da zeólita ZSM-5 com adição de sementes, empregando-se diferentes fontes de silício / Synthesis of ZSM-5 with addition of seeds, up using different sources of silica

Mendonça, Thayane Regine Dantas de 18 June 2013 (has links)
The ZSM-5 zeolite is used in various processes in the petroleum refining and petrochemical, this is possible due to properties such as acid catalyst and high hydrothermal stability. Whereas it is a material of great commercial interest, it is essential that synthesize zeolite in the absence of organic compounds (SDAs), a factor that increases the production cost of these materials. Thus it is necessary the development of new synthetic methodologies for obtaining this material more economically. In this context, the aim of the study was to synthesize ZSM-5 zeolite by hydrothermal method by varying several parameters, such as silica source, SAR, OH/SiO2 reason, utilization of seeds and crystallization time in order to achieve shorter times in the formation of crystalline material. In the synthesis of these materials were used: aluminum sulphate octadecahydrate as an aluminum source, silica gel, sodium silicate as silicon source, sodium hydroxide as sodium source and sulfuric acid. Samples of commercial ZSM-5 CBV 2314 were also employed in the synthesis gel as crystallization seeds. All samples synthesized were characterized by XRD. However, only the sample used as a reference standard was also characterized by FT-IR, TG / DTA and BET in order to understand its physicochemical properties. The XRD analyses indicated the formation of ZSM-5 zeolite for all sources of silica used, however, best results were obtained with sodium silicate as a precursor source of silicon, SiO2/Al2O3 ratio = 50. The samples with the SAR’s 25 and 100 obtained concurrent phases at times greater than 15 and 24 hours, respectively. The spectra in the infrared region confirmed absorption bands characteristic of ZSM-5 zeolite. The thermal analysis showed two stages of weight loss, the first related to the removal of physically adsorbed water and the second to the desorption of the molecule of ammonia, as ZSM-5 commercial in its ammonia form was used as a seed. The results of BET, in turn, showed type I isotherm and high value of specific area, typical characteristics of microporous solids. In microscopy, it could be observed crystallites in the prismatic form with different sizes in length, consistent with the literature. The results showed that synthetic methodologies were effective in formations of crystals of ZSM-5. In this sense, this study showed the sodium silicate as silicon source most appropriate with SiO2/Al2O3 ratio = 50, OH/SiO2 = 0.15 and 10% of seeds, which revealed 100% of crystalline material in 13 hours of synthesis to 170 °C. So, it was possible to propose a plausible rout of synthesis to the zeolite studied. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A zeólita ZSM-5 é utilizada em diversos processos no refino de petróleo e petroquímica, isso devido as suas propriedades como catalisador ácido e elevada estabilidade hidrotérmica. Por ser um material de grande interesse comercial, torna-se indispensável sintetizar esta zeólita na ausência de compostos orgânicos (SDA's), fator que encarece os custos de produção desses materiais. Deste modo se faz necessário o desenvolvimento de novas metodologias de síntese para a obtenção deste material de forma mais econômica. Nesse contexto, o objetivo do estudo foi sintetizar a zeólita ZSM-5 pelo método hidrotérmico variando diversos parâmetros, tais como, fonte de sílica, SAR, razão OH/SiO2, utilização de sementes e tempo de cristalização com a finalidade de alcançar menores tempos de formação do material cristalino. Nas sínteses desses materiais foram utilizados: sulfato de alumínio octadecahidratado como fonte de alumínio, sílicas gel, pirolítica e silicato de sódio como fonte de silício, hidróxido de sódio como fonte de sódio e ácido sulfúrico. Também foram empregadas no gel de síntese amostras de ZSM-5 comercial CBV 2314 como sementes de cristalização. Todas as amostras sintetizadas foram caracterizadas por DRX. Porém, apenas a amostra utilizada como padrão de referência foi caracterizada também por FT-IR, TG/DTA e BET a fim de compreender suas propriedades físico-químicas. As análises de DRX indicaram a formação da zeólita ZSM-5 para todas as fontes de sílica utilizadas, no entanto, foram obtidos melhores resultados com o silicato de sódio como fonte precursora de silício, com razão SiO2/Al2O3=50. As amostras com os SAR’s 25 e 100 obtiveram fases concorrentes para as amostras em tempos superiores a 15 e 24 horas, respectivamente. Os espectros na região do infravermelho confirmaram as bandas de absorção características da zeólita ZSM-5. As análises térmicas apresentaram duas etapas de perda de massa, a primeira relacionada à remoção de água fisicamente adsorvida e a segunda à dessorção de moléculas de amônia, já que a ZSM-5 comercial em sua forma amoniacal foi utilizada como semente. Os resultados de BET por sua vez, revelaram isoterma do tipo I e valor da área específica elevado, características típicas de sólidos microporosos. Nas microscopias, puderam-se observar cristalitos na forma prismática, com diferentes tamanhos de comprimento, concordando com a literatura. Os resultados mostraram que as metodologias de síntese foram eficazes na formação de cristais da ZSM-5. Visto isso, este estudo evidenciou o silicato de sódio como fonte de silício mais adequada com razão SiO2/Al2O3=50, OH/SiO2=0,15 e 10% de sementes, onde se obteve o material 100% cristalino em 13 horas de síntese a 170 ºC. Logo, foi possível propor uma plausível rota de síntese para a zeólita estudada.

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