Made available in DSpace on 2015-05-14T13:21:44Z (GMT). No. of bitstreams: 1 parte1.pdf: 1266396 bytes, checksum: a4c7a57bd0fd6230873b3e69c5c52c4f (MD5) Previous issue date: 2010-12-01 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Molecular sieves have been applied to the processing of triacylglycerols, to produce biofuels. In this context, the mesoporous catalyst Al-MCM-41 was proposed in this work as an alternative to acid heterogeneous transesterification of cottonseed oil with ethanol. This material was prepared using various Si/Al molar ratios (25, 50, 75 and 100) with reaction times of 8, 10, 12 or 14 hours at 170°C. The solids were characterized by XRD, FTIR, 29 Si and 27Al MAS NMR, TG/DTA and nitrogen adsorption, which confirmed the mesoporous phase and allowed an estimate of the acidity associated whit the increase of aluminum content in the structure of MCM-41. The catalytic runs were carried out in a PAAR 4843 reactor, with an oil:ethanol molar ratio of 1:9 and catalyst loading of 1,5% at 200°C for 0-180 min; the reaction product was characterized by gas chromatography and 1H and 13C NMR. Gas chromatographic analysis, shoed that the conversion to ethyl esters is linearly dependent on catalyst loading, and Al-MCM-41 (Si/Al=50) was the most active material under the conditions tested. The results of GC-FID and 1H NMR analysis were corroborated by thermal analysis (TGA) and FTIR measurements, which were used to evaluate the Brønsted acidity of the materials. Overall, the yeld of the fatty acid ethyl ester (FAEE) transesterification increased with an increase in catalyst acidity. / Peneiras moleculares têm sido aplicadas para o processamento de triacilgliceróis, visando à produção de biocombustíveis. Nesse contexto, no presente trabalho, o catalisador mesoporoso Al-MCM-41 foi proposto como uma alternativa para a transesterificação ácida heterogênea do óleo de algodão com etanol. Esse material foi preparado variando a razão molar Si/Al (25, 50, 75 e 100) nos tempos de 8, 10, 12 e 14 horas sob temperatura de 170°C. Os sólidos obtidos foram caracterizados por DRX, FTIR, RMN MAS 29Si e 27Al, TG/DTA e área superficial por adsorção de nitrogênio, de modo que se pôde confirmar a fase mesoporosa e estimar a acidez gerada do incremento de alumínio na estrutura do MCM-41. O teste catalítico foi realizado num reator PAAR 4843, com razão molar óleo:etanol de 1:9, 1,5% de catalisador, a 200°C nos tempos de 0-180 min., sendo o produto obtido caracterizado por cromatografia gasosa e RMN 1H e 13C. Através da análise cromatográfica pôde-se verificar que os catalisadores apresentaram perfis lineares de conversão em etil ésteres, sendo o Al-MCM-41 (Si/Al=50) o material mais ativo nas condições utilizadas. Os resultados observados por CG-FID e RMN 1H, foram corroborados pela análise térmica (TG) e FTIR previstos para a geração de acidez de Bronsted, mostrando que o rendimento em FAEE da reação de transesterificação etílica aumenta com o incremento da acidez nos catalisadores.

SANTOS, Evânia Carvalho dos. Síntese e caracterização de Al-MCM-41 a partir de caulim por rota hidrotérmica e avaliação de desempenho na adsorção de azul de metileno. 2015. 82 f. Dissertação (mestrado em química)- Universidade Federal do Ceará, Fortaleza-CE, 2015. / Submitted by Elineudson Ribeiro (elineudsonr@gmail.com) on 2016-04-01T20:08:54Z No. of bitstreams: 1 2016_dis_ecsantos.pdf: 3288362 bytes, checksum: 7cd0dc9b77f3e67dec527a51e78e5315 (MD5) / Approved for entry into archive by José Jairo Viana de Sousa (jairo@ufc.br) on 2016-05-20T17:34:59Z (GMT) No. of bitstreams: 1 2016_dis_ecsantos.pdf: 3288362 bytes, checksum: 7cd0dc9b77f3e67dec527a51e78e5315 (MD5) / Made available in DSpace on 2016-05-20T17:34:59Z (GMT). No. of bitstreams: 1 2016_dis_ecsantos.pdf: 3288362 bytes, checksum: 7cd0dc9b77f3e67dec527a51e78e5315 (MD5) Previous issue date: 2015 / The mesoporous materials Al-MCM-41 produced from kaolin, low cost raw material, by means of hydrothermal acid treatment route, has shown potential for being used as adsorbent in removal process of methylene blue. The process of synthesis of Al-MCM-41 is based on calcination of kaolin, dealumination by acid treatment, hydrothermal synthesis and extraction of the surfactant. The characterization of de obtained mesoporous material was carried out by techniques such as: X-ray diffraction, vibrational spectroscopy in the infrared, 29Si and 27Al nuclear magnetic resonance in the solid state, scanning electron microscopy, transmission electron microscopy and N2 adsorption/desorption. The X-ray diffraction at low angles allowed the determination of the cell parameter, which was 4.02 nm. The analyses of scanning and transmission electron microscopy revealed important morphological properties of the synthesized material. N2 adsorption/desorption showed a BET specific surface area of 1,303 m2 g-1, pore volume of 1.23 cm3 g-1 and average diameter of 2.45 nm. PZC measurements showed a pHPZC of 2.69. The adsorption of methylene blue by Al-MCM-41 adsorbent showed high kinetic and high adsorption capacity, with values around 316 mg g-1. / O material mesoporoso Al-MCM-41 produzido a partir de caulim, matéria-prima de baixo custo, por meio de rota hidrotérmica com tratamento ácido, mostrou-se promissor para ser usado como adsorvente do corante azul de metileno. O processo de síntese da Al-MCM-41 é baseado na calcinação do caulim, desaluminização por tratamento ácido, síntese hidrotérmica e eliminação do surfactante. A caracterização do material mesoporoso foi realizada por meio de técnicas como: difração de raios-X, espectroscopia vibracional na região do infravermelho, ressonância magnética nuclear no estado sólido de 29Si e 27Al, microscopia eletrônica de varredura, microscopia eletrônica de transmissão e adsorção de N2. A análise de difração de raios-X em baixo ângulo da Al-MCM-41 permitiu a determinação do parâmetro de célula que apresentou valor de 4,02 nm. As análises de microscopia eletrônica de varredura e de transmissão revelaram importantes propriedades morfológicas do material sintetizado. Utilizando as medidas de adsorção e desorção de gás N2 a área superficial específica BET da Al-MCM-41 apresentou valor 1.303 m2 g-1, com um volume de poros de 1,23 cm3 g-1 e diâmetro médio de 2,45 nm. O teste do PZC determinou um pHPZC de 2,69. Os testes de adsorção do azul de metileno pelo adsorvente Al-MCM-41 mostraram que o mesmo apresenta alta capacidade de adsorção com valores em torno de 316 mg g-1.

Made available in DSpace on 2014-12-17T14:08:49Z (GMT). No. of bitstreams: 1 AruzzaMMA_DISSERT.pdf: 1774693 bytes, checksum: a3fe2aad8bc5ee5d62f0d84e6a4733c6 (MD5) Previous issue date: 2011-07-01 / The use of biofuels remotes to the eighteenth century, when Rudolf Diesel made the first trials using peanut oil as fuel in a compression ignition engine. Based on these trials, there was the need for some chemical change to vegetable oil. Among these chemical transformations, we can mention the cracking and transesterification. This work aims at conducting a study using the thermocatalytic and thermal cracking of sunflower oil, using the Al-MCM-41 catalyst. The material type mesoporous Al-MCM-41 was synthesized and characterized by Hydrothermical methods of X-ray diffraction, scanning electron microscopy, nitrogen adsorption, absorption spectroscopy in the infrared and thermal gravimetric analysis (TG / DTG).The study was conducted on the thermogravimetric behavior of sunflower oil on the mesoporous catalyst cited. Activation energy, conversion, and oil degradation as a function of temperature were estimated based on the integral curves of thermogravimetric analysis and the kinetic method of Vyazovkin. The mesoporous material Al-MCM-41 showed one-dimensional hexagonal formation. The study of the kinetic behavior of sunflower oil with the catalyst showed a lower activation energy against the activation energy of pure sunflower oil. Two liquid fractions of sunflower oil were obtained, both in thermal and thermocatalytic pyrolisis. The first fraction obtained was called bio-oil and the second fraction obtained was called acid fraction. The acid fraction collected, in thermal and thermocatalytic pyrolisis, showed very high level of acidity, which is why it was called acid fraction. The first fraction was collected bio-called because it presented results in the range similar to petroleum diesel / O uso dos biocombust?veis remota ao s?culo XVIII, quando Rudolf Diesel realizou os primeiros ensaios utilizando o ?leo de amendoim como combust?vel em um motor de igni??o por compress?o. Com base nesses ensaios, constatou-se a necessidade de realizar algumas transforma??es qu?micas ao ?leo vegetal. Dentre essas transforma??es qu?micas, pode-se citar a transesterifica??o e o craqueamento. Este trabalho tem como objetivo, realizar um estudo utilizando-se o craqueamento t?rmico e termocatal?tico do ?leo de girassol, utilizando o Al-MCM-41 como catalisador. O material mesoporoso tipo Al-MCM-41 foi sintetizado hidrotermicamente e caracterizado pelos m?todos de difra??o de raios-X, microscopia eletr?nica de varredura, adsor??o de nitrog?nio, espectroscopia de absor??o na regi?o do infravermelho e an?lise termogravim?trica (TG/DTG). Ainda foi realizado o estudo do comportamento termogravim?trico do ?leo de girassol sobre o catalisador mesoporoso citado. Com base nas curvas integrais das an?lises termogravim?tricas e o m?todo cin?tico de Vyazovkin, foram estimados a energia de ativa??o, a convers?o e a degrada??o do ?leo em fun??o da temperatura. O material mesoporoso Al-MCM-41 apresentou forma??o hexagonal unidimensional. O estudo do comportamento cin?tico do ?leo de girassol com o catalisador mostrou uma menor energia de ativa??o frente ? energia de ativa??o do ?leo de girassol puro. Na pir?lise t?rmica e termocatal?tica do ?leo de girassol foram obtidas duas fra??es l?quidas. A primeira fra??o obtida foi denominada de bio?leo e a segunda fra??o obtida foi denominada de fra??o ?cida. A fra??o ?cida coletada tanto na pir?lise t?rmica como na termocatal?tica apresentou ?ndice de acidez muito elevado, raz?o pela qual foi denominada fra??o ?cida. A primeira fra??o coletada foi denominada de bio?leo porque apresentou resultados na faixa semelhante ao diesel de petr?leo

Made available in DSpace on 2014-12-17T15:42:27Z (GMT). No. of bitstreams: 1 AlineAAO_TESE.pdf: 3075922 bytes, checksum: bd3bdc6aafacdcbe05784c0fbe751097 (MD5) Previous issue date: 2013-08-09 / The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API ? equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ? C and heating ratios (β) ranging from 5, 10 and 20 ?C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41 / Os materiais mesoporosos nanoestruturados vem sendo estudados para aplica??o na ind?stria do petr?leo, em especial o Al-MCM-41, devido ? ?rea superficial em torno de 800-1000 m2g-1 e di?metro de poros variando de 2 a 10 nm, adequado para cat?lise de mol?culas grandes como petr?leos pesados. O MCM-41 foi sintetizado pelo m?todo hidrot?rmico, o qual foi adicionado Alum?nio numa propor??o Si/Al igual ? 50, a fim de aumentar a gera??o de s?tios ?cidos ativos nos nanotubos. O catalisador foi caracterizado por difra??o de Raios-X (DRX), ?rea superficial pelo m?todo BET e volume m?dio de poros pelo m?todo BJH atrav?s da adsor??o de N2, espectroscopia de absor??o na regi?o do infravermelho por Transformada de Fourier (FT-IR) e determina??o da acidez superficial com aplica??o de uma mol?cula sonda nbutilamina. O catalisador apresentou propriedades estruturais bem definidas e coerentes com a literatura. O objetivo geral foi testar o Al-MCM-41 como catalisador e realizar ensaios termogravim?tricos, utilizando duas amostras de petr?leo pesado com ?API iguais ? 14,0 e 18,5. Os ensaios foram realizados usando uma faixa de temperatura de 30 900?C, e raz?es de aquecimento (β) variando de 5, 10 e 20 ?Cmin-1. O intuito era verificar os perfis termogravim?tricos destes petr?leos quando submetidos ? a??o do catalisador Al-MCM-41. Para tanto, variou-se o percentual de catalisador aplicado in situ: 1, 3, 5, 10 e 20% em massa e, a partir dos dados termogravim?tricos foram aplicados dois modelos cin?ticos diferentes: Ozawa-Flynn-Wall (OFW) e Kissinger- Akahrira-Sunose (KAS). As energias de ativa??o aparente encontradas para ambos os modelos tinham valores semelhantes e eram menores para o segundo evento de perda de massa conhecido como zona de craqueamento, indicando uma atua??o mais efetiva do Al-MCM-41 nessa zona. Al?m disso, constatou-se uma diminui??o mais acentuada no valor das energias de ativa??o para valores entre 10 e 20% em massa da mistura catalisador-?leo. Concluiu-se que o Al-MCM-41 possui aplicabilidade catal?tica em petr?leos pesados diminuindo a energia de ativa??o aparente de um sistema catalisador?leo, sendo o melhor resultado com 20% em massa de Al-MCM-41

Une nouvelle approche de synthèse a été développée pour non seulement contrôler la morphologie, la taille et la texture de particules de silice mais aussi incorporer une ou plusieurs fonctionnalités à la surface interne de leurs pores. La morphologie sphérique, la monodispersité des particules, la porosité radiale, la dispersion et l'accessibilité des fonctionnalités ainsi que leur taux d'incorporation constituent les propriétés et les paramètres physico-chimiques privilégiés dans notre approche qui est basée sur la méthode de Stöber modifiée et la fonctionnalisation in-situ. Deux différentes applications ont été retenues pour étudier la quintessence de cette approche. La première consiste à incorporer des espèces métalliques (Al et Cu par exemple) dans les sphères de silice afin de les rendre fonctionnelles pour des applications catalytiques en phase liquide; et la deuxième consiste à greffer à la surface des particules des nanomachines sensibles permettant de contrôler le relargage des molécules actives pour des applications thérapeutiques. Dans les deux cas d'application, des performances optimales sont attendues. / A novel approach of synthesis has been developed in order to control simultaneously the morphology, size and textural parameters of silica particles, as well as to incorporate one or more functional groups in the pore walls. In this approach, based on the modified Stöber method and in-situ functionalization, emphasis is put on the spherical morphology, the particle monodispersity, the radially disposed porous structure, and the appropriate dispersion and accessibility of surface functional groups. Two potential applications have been selected so as to verify the feasibility of the approach. In view of materials use for heterogenous catalysis in the liquid phase, the monodisperses mesoporous silica spheres were derivatized with metallic species (e.g., Al and Cu) by direct incorporation in the synthesis stage. The second type of applications concerned the use of silica spheres as sensitive nanomachines for the controlled drug release and required grafting of appropriate organic molecules onto the silica surface.

The mesoporous materials Al-MCM-41 produced from kaolin, low cost raw material, by means of hydrothermal acid treatment route, has shown potential for being used as adsorbent in removal process of methylene blue. The process of synthesis of Al-MCM-41 is based on calcination of kaolin, dealumination by acid treatment, hydrothermal synthesis and extraction of the surfactant. The characterization of de obtained mesoporous material was carried out by techniques such as: X-ray diffraction, vibrational spectroscopy in the infrared, 29Si and 27Al nuclear magnetic resonance in the solid state, scanning electron microscopy, transmission electron microscopy and N2 adsorption/desorption. The X-ray diffraction at low angles allowed the determination of the cell parameter, which was 4.02 nm. The analyses of scanning and transmission electron microscopy revealed important morphological properties of the synthesized material. N2 adsorption/desorption showed a BET specific surface area of 1,303 m2 g-1, pore volume of 1.23 cm3 g-1 and average diameter of 2.45 nm. PZC measurements showed a pHPZC of 2.69. The adsorption of methylene blue by Al-MCM-41 adsorbent showed high kinetic and high adsorption capacity, with values around 316 mg g-1. / O material mesoporoso Al-MCM-41 produzido a partir de caulim, matÃria-prima de baixo custo, por meio de rota hidrotÃrmica com tratamento Ãcido, mostrou-se promissor para ser usado como adsorvente do corante azul de metileno. O processo de sÃntese da Al-MCM-41 Ã baseado na calcinaÃÃo do caulim, desaluminizaÃÃo por tratamento Ãcido, sÃntese hidrotÃrmica e eliminaÃÃo do surfactante. A caracterizaÃÃo do material mesoporoso foi realizada por meio de tÃcnicas como: difraÃÃo de raios-X, espectroscopia vibracional na regiÃo do infravermelho, ressonÃncia magnÃtica nuclear no estado sÃlido de 29Si e 27Al, microscopia eletrÃnica de varredura, microscopia eletrÃnica de transmissÃo e adsorÃÃo de N2. A anÃlise de difraÃÃo de raios-X em baixo Ãngulo da Al-MCM-41 permitiu a determinaÃÃo do parÃmetro de cÃlula que apresentou valor de 4,02 nm. As anÃlises de microscopia eletrÃnica de varredura e de transmissÃo revelaram importantes propriedades morfolÃgicas do material sintetizado. Utilizando as medidas de adsorÃÃo e desorÃÃo de gÃs N2 a Ãrea superficial especÃfica BET da Al-MCM-41 apresentou valor 1.303 m2 g-1, com um volume de poros de 1,23 cm3 g-1 e diÃmetro mÃdio de 2,45 nm. O teste do PZC determinou um pHPZC de 2,69. Os testes de adsorÃÃo do azul de metileno pelo adsorvente Al-MCM-41 mostraram que o mesmo apresenta alta capacidade de adsorÃÃo com valores em torno de 316 mg g-1.

Diese Arbeit befasst sich mit der katalytischen Umsetzung von oxygenierten Kohlenwasserstoffen in einem Strömungsrohrreaktor bei 500 °C an mikroporösem Alumosilicat ZSM-5, an dem mesoporösem Alumosilicat Al-MCM-41 sowie an deren Mischphasen. Anhand der katalytischen Untersuchungen ist es möglich, für verschiedene Anforderungen an das Produktspektrum Empfehlungen an die Eigenschaften des zu verwendeten Katalysatorsystems zu formulieren. Hierfür wurden Untersuchungen zum Einfluss relevanter Syntheseprozessparameter auf die Zusammensetzung von Al-MCM-41/ZSM-5-Mischphasen vorgenommen. Die Synthese solcher Mischphasen wurde über einen 'Zwei-Template/Ein-Schritt“-Ansatz durchgeführt, der es erlaubte, die an das Katalysatorsystem gestellten Anforderungen durch eine geeignete Wahl der Syntheseparameter zu genügen. Während der Synthese der Al-MCM-41/ZSM-5-Mischphasen beobachtet man drei sich gegenseitig beeinflussenden Vorgänge, die durch, in der wässrigen Syntheselösung vorliegende, alumosilicatische Komponenten miteinander verknüpft sind: Die Auflösung und anschließende Restrukturierung einer nicht-porösen amorphen Phase, die Auflösung und Restrukturierung einer mesoporösen Al-MCM-41-Phase und die Kristallisation einer mikroporösen ZSM-5-Phase. Durch die Erhöhung des Al-Anteils im Synthesegel werden die ZSM-5-Kristallisation verlangsamt und der Schwerpunkt des Gleichgewichts dieser drei Vorgänge für einen gegebenen Reaktionszeitpunkt in Richtung der Bildung der mesoporösen Al-MCM-41-Phase verlagert. Der Einfluss des, in das jeweilige Katalysatorsystem eingebauten Aluminiums auf die katalytische Umsetzung von Oxygenaten manifestiert sich für die beiden Alumosilicate ZSM¬ 5 und Al MCM-41 auf verschiedene Weise. Eine Erhöhung des Al-Anteils in einem mikroporösen ZSM-5-Katalysatorsystem begünstigt den Verlauf von bimolekularen Reaktionen. Dies äußert sich in einem verstärkten Auftreten von Paraffin-bildenden Raktionen wie die Wasserstoff-Transfer-Reaktionen und/oder die Carboniumionen-Spaltung sowie in einer Dominanz von Aromaten-bildenen Reaktionen wie die Cyclisierung mit anschließender Dehydrierung und Aromatisierung. Dieser Effekt kann bei einer Erhöhung des Al-Anteils in einem mesoporösen Al-MCM-41-Katalysatorsystem nur im geringen Maße beobachtet werden. Jedoch nimmt mit sinkendem Si/Al-Verhältnis in beiden Katalysatorsystemen der Anteil an Produkten mit drei oder vier Kohlenstoffatomen zu. Zudem kann dabei eine beginnende Unabhängigkeit des gebildeten Produktspektrums von der Kettenlänge und der funktionellen Gruppe des umgesetzten Oxygenats beobachtet werden.:Inhaltsverzeichnis 1 Einleitung und Problemstellung 1 2 Grundlagen 4 2.1 Hydrothermale Synthese von Alumosilicaten 4 2.1.1 WÄSSRIGE CHEMIE UND HYDROTHERMALE BEHANDLUNG VON ALUMOSILICATEN 4 2.1.2 STRUKTUR UND BILDUNGSMECHANISMUS VON AL-MCM-41 5 2.1.3 STRUKTUR UND BILDUNGSMECHANISMUS VON ZSM-5 6 2.2 Katalytische Spaltung von Kohlenwasserstoffen an Alumosilicaten 9 2.2.1 NATUR UND LOKALISIERUNG VON SÄUREZENTREN 9 2.2.2 KOHLENWASSERSTOFF-POOL-MECHANISMUS UND VERKOKUNG 10 3 Experimentelles Vorgehen und analytische Messverfahren 14 3.1 Syntheseroute zur Herstellung von Al MCM 41/ZSM 5-Mischphasen, Al MCM 41 und ZSM-5 14 3.1.1 AL MCM 41/ZSM 5 MISCHPHASEN 14 3.1.2 AL-MCM-41 17 3.1.3 ZSM-5 17 3.2 Datenerhebung und -auswertung relevanter physikalisch-chemischer und festkörperanalytischer Charakterisierungsmethoden 17 3.2.1 PULVER-RÖNTGENDIFFRAKTOMETRIE 17 3.2.2 N2-PHYSISORPTION 19 3.2.3 TEMPERATUR-PROGRAMMIERTE AMMONIAK-DESORPTION 21 3.2.4 ELEMENTARANALYSE 23 3.2.5 27AL MAS NMR 24 3.2.6 THERMOGRAVIMETRISCHE ANALYSE 25 3.3 Katalytische Austestung und Analyse der Messdaten 26 3.3.1 VERSUCHSDURCHFÜHRUNG 26 3.3.2 ANALYSE UND AUSWERTUNG KATALYTISCHER MESSDATEN 27 3.3.3 DURCHGEFÜHRTE KATALYTISCHE TESTMESSUNGEN 29 4 Untersuchungen zum Bildungsmechanismus von Al MCM 41/ZSM 5-Mischphasen 33 4.1 Mechanistische Deutung 33 4.1.1 VORBETRACHTUNG 33 4.1.2 REAKTIONSABLAUF 34 4.1.3 UNTERSUCHUNG DER MESOPOROSITÄT 39 4.1.4 MORPHOLOGISCHE BETRACHTUNG 43 4.2 Wechselwirkungen der „Beeinflussungsfaktoren“ 45 4.2.1 EFFEKT VERSCHIEDENER AUTOKLAV-TYPEN 45 4.2.2 EFFEKT DES AL-ANTEILS IM SYNTHESEGEL 48 4.2.3 SYMBIOTISCHE EINFLUSSNAHME VON ALUMINIUM UND TENSIDEN 50 5 Charakterisierung verwendeter Katalysatormaterialien 52 5.1 ZSM-5 52 5.2 Al-MCM-41 57 5.3 Physikalische Mischungen aus Al-MCM-41 und ZSM-5 60 6 Katalytisches Spalten von Oxygenaten an ZSM 5 64 6.1 Katalytisches Spalten von Alkohol-Oxygenaten an ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 64 6.1.1 PRODUKTANALYSE ANHAND DER KOHLENSTOFFANZAHL IM PRODUKTMOLEKÜL 65 6.1.2 PRODUKTANALYSE ANHAND EINZELNER STOFFGRUPPEN 68 6.2 Katalytisches Spalten von Carbonyl-Oxygenaten an ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 71 6.2.1 PRODUKTANALYSE ANHAND DER KOHLENSTOFFANZAHL IM PRODUKTMOLEKÜL 72 6.2.2 PRODUKTANALYSE ANHAND EINZELNER STOFFGRUPPEN 76 6.3 Ableitung eines Kohlenwasserstoff-Pool Mechanismus zur Beschreibung des katalytischen Spaltens von Oxygenaten an ZSM 5 80 6.3.1 VEREINHEITLICHUNG DES OXYGENAT FEEDS ÜBER DESSEN DEOXYGENIERUNG 81 6.3.2 ASSIMILATION KURZKETTIGER OLEFINE DURCH EINEN KATALYTISCH AKTIVEN BEREICH 83 6.3.3 EINFLUSS DES PORENSYSTEMS UND AL-ANTEILS IM KATALYSATORSYSTEMS 85 6.3.4 BESCHREIBUNG DER PRODUKTBILDUNG EINZELNER STOFFGRUPPEN IN ABHÄNGIGKEIT WESENTLICHER REAKTIONSBEDINGUNGEN 87 7 Katalytisches Spalten von Triacylglyceriden an Al MCM 41 und physikalischen Mischungen aus Al-MCM-41 und ZSM-5 92 7.1 Gegenüberstellung des katalytischen Spaltens von Ethyloctanoat an Al MCM 41 und ZSM 5 in Abhängigkeit des Si/Al Verhältnisses 92 7.2 Anwendung des Kohlenwasserstoff-Pool Mechanismus zur Beschreibung des katalytischen Spaltens von Triacylglyceriden an physikalischen Mischungen aus Al MCM-41 und ZSM-5 97 7.3 Synthese-Struktur-Wirkungsprinzip 103 8 Zusammenfassung und Ausblick 106 Literatur 112 Abbildungsverzeichnis 127 Tabellenverzeichnis 139 Abkürzungsverzeichnis 141 Anhang 142 Veröffentlichungen 165 Eidesstattliche Erklärung 168

Made available in DSpace on 2014-12-17T15:41:47Z (GMT). No. of bitstreams: 1 KesiaKV.pdf: 2272602 bytes, checksum: 46f23a52fbc9d4e74dfd9f25d2f58e11 (MD5) Previous issue date: 2009-02-19 / In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamar?- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products / No presente trabalho, foram sintetizados materiais mesoporos da fam?lia M41S que foram descobertos no in?cio dos anos 90 por pesquisadores da Mobil Oil Corporation, possibilitando assim novas perspectivas no ramo da cat?lise. Um dos mais importantes membros desta fam?lia ? o MCM-41, que possui um arranjo hexagonal de mesoporos com di?metros de poros entre 2 a 10 nm e uma alta ?rea superficial, tornando-o bastante promissor para ser utilizado como catalisador no refino do petr?leo para o craqueamento catal?tico, j? que seus mesoporos facilitam o acesso de mol?culas grandes de hidrocarbonetos, aumentando assim a produ??o de produtos leves com uma alta demanda no mercado. A adi??o de alum?nio na estrutura do MCM-41 aumenta a acidez do material, tornando-o mais positivo para aplica??o na ind?stria petroqu?mica. Os materiais mesoporosos do tipo MCM-41 e Al-MCM- 41 (raz?o Si/Al=50) foram sintetizados atrav?s do m?todo hidrot?rmico partindo da S?lica gel, NaOH e ?gua destilada. Como direcionador estrutural foi utilizado CTMABr. Para o Al- MCM-41 utilizaram-se os mesmos reagentes acrescentando a pseudobohemita (fonte de alum?nio) no gel de s?ntese. As s?nteses foram realizadas durante um per?odo de quatro dias com corre??o di?ria de pH. As melhores condi??es de calcina??o para remo??o do direcionador org?nico (CTMABr) foram otimizadas por TG/DTG e atrav?s de an?lises por DRX, FTIR e adsor??o de nitrog?nio verificou-se que tanto o m?todo de s?ntese hidrot?rmica como as condi??es de calcina??o baseado nos estudos por TG foram promissores para produ??o de materiais mesoporosos com alto grau de ordena??o hexagonal. As propriedades ?cidas dos materiais foram determinadas pela dessor??o de n- butilamina via termogravimetria. Comprovou-se que a adi??o de alum?nio na estrutura do MCM-41 promoveu um aumento na acidez deste catalisador. Para verificar a atividade catal?tica desses materiais utilizou-se uma amostra do Res?duo Atmosf?rico (RAT) que ? proveniente da destila??o atmosf?rica do petr?leo proveniente do P?lo de Guamar?- RN previamente caracterizado por v?rias t?cnicas como: Termogravimetria, FTIR e FRX, realizando-se atrav?s da an?lise t?rmica um estudo comparativo entre a degrada??o t?rmica do RAT, pir?lise do RAT+MCM-41 e RAT+Al-MCM-41. Verificou-se que o Al-MCM-41 promoveu um efeito catal?tico mais satisfat?rio na pir?lise do RAT, j? que o craqueamento dos produtos pesados presentes no res?duo ocorreu em temperaturas inferiores ?s observadas para a pir?lise com MCM-41 e com isso diminuindo tamb?m a energia de ativa??o para o processo, bem como aumentando os valores de convers?o do res?duo em produtos leves

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-05-30T22:35:16Z No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-01T20:17:58Z (GMT) No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) / Made available in DSpace on 2016-06-01T20:17:58Z (GMT). No. of bitstreams: 1 EnedersonRossetto_TESE.pdf: 3942346 bytes, checksum: 4f772d5bb76c7fedad3ac6471650a54d (MD5) Previous issue date: 2015-07-31 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Os ligantes ?-diiminas 2-(fenil)amino-4-(fenil)imino-2-penteno e o 2-(2,6-dimetilfenil)amino-4-(2,6-dimetilfenil)imino-2-penteno foram combinados com o grupo alcoxisilano cloropropiltrimetoxisilano (CPTMS) e ancorado covalentemente aos suportes mesoporosos MCM-41 e SBA-15, coordenados pela intera??o com os grupos silan?is da matriz das s?licas e complexados com n?quel. Os complexos Ni-?-diimina/mesoporosos foram sintetizados para aplica??o em rea??es de oligomeriza??o do etileno e do propileno e para compara??o dos resultados entre o sistema homog?neo com o sistema heterog?neo. O suporte foi primeiramente sintetizado e calcinado. Ap?s foi realizado o ancoramento dos ligantes e posterior complexac?o do n?quel. Estes materiais foram caracterizados por v?rias t?cnicas, tais como: RMN de 1H, 13C e 29Si, DRX de baixo ?ngulo, Infra-vermelho (IR), an?lise termogravim?trica, an?lise de isotermas de adsor??o-dessor??o de N2, microscopia eletr?nica de transmiss?o (MET) e de varredura (MEV), an?lise elementar e espectroscopia de absor??o at?mica para confirmar o sucesso das s?nteses dos materiais. Ambos os complexos homog?neos e os heterogeneizados s?o ativos e seletivos para as rea??es de oligomeriza??o do etileno e do propileno. Os materiais heterogeneizados foram menos ativos que os complexos an?logos homog?neos nas rea??es de oligomeriza??o do etileno, por?m, foram mais seletivos tanto para fra??es C4 quanto para ?-C4. Nas rea??es com o propileno os complexos homog?neos promoveram ? rea??o de dimeriza??o e os complexos heterogeneizados ? rea??o de alquila??o do tolueno com o propileno. / The ?-diimine ligands 2-(phenyl)amine-4-(phenyl)imine-2-pentene and 2-(2,6- dimethylphenyl)amine-4-(2,6-dimethylphenyl)imine-2-pentene were combined with the alkoxysilane group chloropropyltrimethoxysilane (CPTMS) and covalently anchored to a mesoporous MCM-41, Al-MCM-41 and SBA-15 support, ordered by interaction with the silanols of the silica matrix and complexed with nickel. The complexes were synthesized for application in ethylene and propylene oligomerization and for comparing results between homogeneous and heterogeneous systems. The support is first synthesized, calcined, anchored to the ligand, and then subsequent complexation of nickel is realized. These materials were characterized by several techniques such as 1H, 13C and 29Si NMR, small angle XRD, Infra-red, thermogravimetric analysis, nitrogen adsorption-desorption isotherms, transmission and scanning electron microscopy, elemental analysis, and flame atomic absorption spectroscopy, to confirm the success of the synthesis. Both homogeneous and heterogeneous complexes are active and selective for the reactions of ethylene and propylene oligomerization. The heterogenized materials were less active than the homogeneous analogous complexes in the reactions of oligomerization of ethylene, however, were more selective for both C4 fractions and for ?-C4. In reactions with propylene, the homogeneous complexes promoted the dimerization reaction and the heterogenized complexes the alkylation reaction of toluene with propylene complex.Complexes were tested in recycle reactions proved to be efficient for use in large scale.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-30T16:37:00Z No. of bitstreams: 1 CLÁUDIA DOURADO MEDEIROS - DISSERTAÇÃO PPGEQ 2014..pdf: 1542895 bytes, checksum: 5a74f0ba9e6514c2859c363f528e0b6f (MD5) / Made available in DSpace on 2018-04-30T16:37:00Z (GMT). No. of bitstreams: 1 CLÁUDIA DOURADO MEDEIROS - DISSERTAÇÃO PPGEQ 2014..pdf: 1542895 bytes, checksum: 5a74f0ba9e6514c2859c363f528e0b6f (MD5) Previous issue date: 2014-04-02 / Capes / As peneiras moleculares mesoporosas possuem um arranjo hexagonal de mesoporos com diâmetros de poros que variam de 2 a 10 nm, possuindo assim uma área superficial elevada. A adição de um metal a sua estrutura tem como função gerar a acidez ao material o tornando mais reativo, aumentado assim a possibilidade do seu uso como catalisador na indústria do petróleo. Atualmente, um dos problemas encontrados pelos pesquisadores para obtenção desse tipo de peneira, é o longo tempo de formação das estruturas. No presente trabalho as peneiras moleculares mesoporosas MCM-41 e Al-MCM-41 foram sintetizadas utilizando dois processos hidrotermais, a tradicional e por micro-ondas, com o objetivo principal de reduzir o tempo de síntese do material. A peneira molecular MCM-41 foi sintetizada utilizando o processo hidrotermal tradicional, 100 oC por 48 horas , como também utilizando o processo hidrotermal de micro-ondas através de três metodologias, adotando diferentes tempos e temperaturas. Tomando como base os resultados obtidos com as sínteses da peneira molecular MCM-41 por meio do método hidrotermal de micro-ondas, os mesmos métodos foram aplicados para a peneira molecular Al-MCM-41 nas mesmas condições de tempo e temperatura. Através dos difratogramas foi possível perceber que a estrutura hexagonal foi formada. Verificouse que o melhor tempo de síntese da Al-MCM-41 se deu com 60 minutos a 130 oC. A partir destes dados, foram realizadas novas sínteses, reduzindo o tempo gradativamente. Os resultados das análises de DRX, MEV e FTIR comprovam que as peneiras moleculares mesoporosas foram formadas, sendo possível identificar sua estrutura e morfologia. Os melhores resultados de síntese para as peneiras moleculares mesoporosas MCM-41 e Al-MCM-41, foram nos tempos 60 e 40 minutos e temperatura de 130 oC, respectivamente. / The mesoporous molecular sieves have a hexagonal arrangement of mesopores with pore diameters ranging from 2 to 10 nm, which implies in a high surface area. The addition of a metal into these structures has the function of generating acidity in the material making it more reactive, increasing the possibility of using it as a catalyst into the oil industry. Nowadays, one of the problems found by researches to obtain these type of molecular sieves is the long time of structure formation taken by these materials. In this study, the mesoporous molecular sieves MCM - 41 and Al -MCM -41 were synthesized using two traditional microwave, with the primary goal of reducing the time of synthesis of the material hydrothermal processes. The molecular sieve MCM -41 was synthesized using the traditional hydrothermal process 100 °C for 48 hours , as well as hydrothermal process using microwave by three methods , adopting different times and temperatures . Based on the results obtained with the synthesis of molecular sieve MCM -41 by hydrothermal microwave method, the same methods were applied to the molecular sieve Al -MCM -41 under the same conditions of time and temperature. Through the DRX patterns was observed that the hexagonal structure was formed. It was found that the best time of synthesis of Al- MCM-41 was given 60 minutes at 130 oC. From these data, new syntheses were carried out by reducing the time gradually. The results of DRX, MEV and FTIR show that the mesoporous molecular sieves were formed, it is possible to identify their structure and morphology. The best results for the synthesis of mesoporous molecular sieves MCM - 41 and Al -MCM -41, were at times 60 and 40 minutes and temperatures of 130 °C, respectively.