[pt] Os catalisadores de platina, níquel e platina suportados em sílica-alumina e sílica mesoporosa (SBA-15) foram investigados para o hidrotratamento do óleo de coco para produção de bio-óleo. Os suportes foram carregados com 1 por cento de Pt e 5 por cento de Ni e os catalisadores resultantes foram caracterizados para determinar suas propriedades estruturais e de textura. Os catalisadores foram reduzidos e testados em um reator semi-descontínuo a 360 C sob 10 MPa de hidrogênio durante 4 horas. Foram obtidos 30-40 por cento de remoção de oxigênio. As curvas de destilação dos produtos e seu ponto de inflamação e gravidade específica (a 20 C) foram determinados pelos métodos oficiais ASTM e ABNT/NBR a serem comparados com o diesel derivado do petróleo. As curvas de destilação e as propriedades físico-químicas foram muito próximas das especificações estabelecidas pela legislação brasileira para o diesel comercial. Destilou-se 90 por cento do volume de cada produto na faixa de temperatura de 180-370 C, o ponto de inflamação ficou entre 76-81 e o número do índice de cetano foi calculado como 47-48, de acordo com as especificações do diesel comercial. Os produtos obtidos com os catalisadores Pt/SiO2Al2O3 e PtNi/SBA-15 também apresentaram gravidade específica dentro da faixa de especificação (865 e 860,0 kg/m3, respectivamente). Os catalisadores utilizados mostraram sua potencial aplicação para a produção de biocombustíveis na faixa de diesel de petróleo pelo processo de hidrotratamento de óleo de coco. / [en] Platinum, platinum nickel and nickel catalysts supported on silicaalumina and mesoporous silica (SBA-15) were investigated for hydrotreating of coconut oil to produce bio oil. The supports were loaded with 1 percent Pt and 5 percent Ni content and the resulted catalysts were caracterized to determine their strutural and textural properties. The catalysts were reduced and tested in a semi-batch reactor at 360 C under 10 MPa of hydrogen during 4 hours. It was obtainned 30-40 percent of oxygen removal. The distillation curves of products and their flash point and specific gravity (at 20 C) were determined by oficials ASTM, and ABNT/NBR methods to be compared with the petroleum-derived diesel. The distillation curves and physicochemical properties were very close to specifications stabilished by Brazilian legislation for comercial diesel. 90 percent of the volume of each product was distilled in the temperature range of 180-370 C, the flash point was between 76-81 and the cetane index number was calculated as 47-48 in agreement with the specifications for comercial diesel. The products obtainned using the Pt/SiO2Al2O3 and PtNi/SBA-15 catalysts also presented specific gravity within the specification range (865 e 860.0 kg/m3 respectively). The catalysts used showed their potential application for the production of biofuels in the petroleum diesel range by coconut oil hydrotreatment process.

[pt] A reação de síntese de Fischer-Tropsch tem despertado interesse pelo seu caráter tecnológico e científico uma vez que este processo é capaz de converter o gás natural em produtos de elevado valor agregado. No presente trabalho, catalisadores de ferro suportados em sílica alumina ou em SBA-15 foram sintetizados, caracterizados, ativados e empregados na síntese de Fischer Tropsch. Os catalisadores foram preparados via impregnação incipiente do ponto úmido utilizando cloreto de ferro III, obtendo-se catalisadores de porcentagem mássica próximos a 5%, 10% e, no caso da sílica alumina, 2% também. As amostras foram caracterizadas por análise termogravimétrica (ATG), por medidas de adsorção física de N2, difração de raios-X (DRX) e redução à temperatura programada (RTP). O teor de ferro foi determinado pela espectroscopia de raios X por dispersão de energia (EDX). A ativação dos catalisadores e, em seguida, os testes catalíticos foram conduzidos em um reator tubular de bancada e os produtos gasosos foram analisados através de cromatografia gasosa com detector por ionização de chama (CG-DIC), cuja análise mostrou a formação de hidrocarbonetos C1-C5. A adsorção física de N2 revelou que, a introdução de ferro nos suportes, diminuiu a área superficial específica e o volume de poro dos materiais. A difração de raios X foi realizada para os catalisadores após a calcinação, mostrando a presença das fases α-Fe2O3 e Fe3O4; após a ativação e após a reação, onde se encontrou Fe0 e carbetos de ferro Fe5C2 e Fe2C. Os testes catalíticos mostraram maior seletividade aos hidrocarbonetos C2-3 para os catalisadores suportados em SBA-15. / [en] The Fischer-Tropsch synthesis reaction has showed interest due to its technological and scientific character since the process is able to convert natural gas into high added value products. In the present work, iron catalysts supported on SBA-15 or silica doped alumina were synthesized, characterized, activated and employed in the Fischer Tropsch synthesis. The catalysts were prepared via incipient wetness impregnation method using iron III chloride, obtaining catalysts with a weight percentage of about 5%, 10% and, in the case of silica doped alumina, 20% as well. The samples were characterized by thermogravimetric analysis (ATG), with measurements of N2 physisorption, X-ray diffraction (DRX) and temperature programmed reduction (RTP). Iron content was determined by energy dispersive X-ray spectroscopy (EDX). The catalysts activation and, subsequently, their catalytic tests were conducted in a bench tubular reactor and the products were analyzed by gas chromatography with flame ionization detector (CG-DIC), where it was detected the formation of C1-C4 hydrocarbons. The N2 physisorption showed that the introduction iron in the supports decreased the specific surface area and the pore volume of the materials. X-ray diffraction was performed for catalysts after calcination, showing the presence of α-Fe2O3 and Fe3O4 phases, after activation and after reaction, where it was found crystals of Fe0 and iron carbides Fe5C2 and Fe2C. The catalytic tests showed greater C2-3 selectivity for SBA-15 supported catalysts.

El plan de investigación se centra en el estudio y diseño de catalizadores híbridos para el proceso de síntesis directa de dimetil éter (DME) a partir de gas de síntesis, también conocido en la literatura como "Syngas-To-DME o STD process" [1]. Para llevar a cabo el proceso de síntesis directa de DME se emplean catalizadores híbridos constituidos por mezclas físicas del componente de síntesis de metanol (catalizador basado en Cu) y el componente ácido que lleva a cabo la deshidratación de metanol para dar lugar al DME (zeolita) [1]. De manera general, las labores en las que se centra el plan de investigación persiguen lograr un mayor entendimiento de las propiedades del catalizador híbrido que determinan su comportamiento en el proceso de síntesis directa de DME (STD), prestando especial atención al componente zeolítico con el cual están asociadas la mayoría de controversias en la literatura científica. / García Trenco, A. (2013). Desarrollo de catalizadores híbridos CuZnOAl2O3/zeolita para el proceso de síntesis directa de DME [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/34781

A range of mesoporous materials based on SBA-15 have been prepared and characterised. The materials were templated by neutral block copolymer P123, and typically have a hexagonal (p6mm) pore structure, with high surface areas and narrow pore size distributions. The removal of the surfactant template by calcination and solvent extraction has been investigated. The aqueous stability of this material, and the hydrolysis of the surface was studied. Organic functional groups were incorporated into the silica surface by co-condensation, or by post synthesis grafting. A range of functional groups were incorporated, including amine, carboxy, allyl and thiol groups. The pore size of the materials was controlled by the addition of trimethoxybenzene during synthesis, which significantly increased the pore size and uptake capacity of the materials. The adsorption of CALB by SBA-15 was investigated, with support materials extracted by calcination or solvent extraction. Rapid uptake at high loading was observed, with a maximum loading of 450 mg g-1 measured. The leaching of the enzyme from the support was investigated, and found to be high with unfunctionalised supports. The leaching from functionalised supports incorporating sulfur groups was significantly reduced. The activity of the immobilised CALB was measured by tributyrin hydrolysis in aqueous media, and by enantioselective transesterification of (R)-1-phenylethanol in organic media. The effect of surface functionalisation for reusability and thermal stability in aqueous systems was investigated. Preliminary studies of supported CALB for dynamic kinetic resolution were carried out, with an investigation of acidic zeolites and a mesoporous supported catalyst for 1-phenylethanol racemisation. The encapsulation of immobilised CALB was investigated, and the activity and reusability of these systems studied.

Uma das desvantagens dos bio-óleos precursores do biodiesel é a alta carga de compostos oxigenados que diminuem seu poder de combustão, reduzindo sua eficiência e inviabilizando seu uso em larga escala. Nesse contexto, o processo de hidrodesoxigenação (HDO) é relevante, dado que elimina esses compostos através de uma reação catalítica e, portanto, aumenta o poder calorífico do combustível. Neste trabalho, estudou-se a HDO do guaiacol (2-metoxifenol) como composto modelo dos bio-óleos derivados da biomassa e avaliou-se o desempenho de catalisadores de Ni e Mo no processo. Estudou-se a performance de um catalisador suportado em SBA-15 - um material mesoporoso de sílica de alta área superficial - em comparação a de um catalisador tradicional suportado em gama-alumina. Para tal, utilizou-se um sistema contínuo em fase gasosa e reator de leito fixo. Utilizaram-se técnicas de caracterização de catalisadores, como adsorção de N2, MEV, MET, DRX, TPR-H2, FTIR, TPO-O2, Raman e TGA. Através das análises DRX e MET, comprovou-se que se formaram partículas de NiO e MoO3 de menor tamanho e mais dispersas no caso do catalisador de SBA-15, devido à menor interação com o suporte e maior área superficial, o que resultou em um grau de redução de 91,6 % deste catalisador, em comparação a 73,4 % do outro, analisados por TPR-H2. Os testes catalíticos mostraram que o catalisador de NiMo/SBA-15 supera o de alumina em termos de conversão no intervalo de 200 a 300 °C, com ciclohexeno e ciclohexano como principais produtos, em face à maior seletividade a catecol e fenol no NiMo/?-Al2O3. A 300 °C, o catalisador suportado em sílica alcançou taxas de 66,5 % para a HDO e 35,3 % HDA (hidrodesaromatização), enquanto o de alumina obteve somente 30,8 e 2,7 %, respectivamente. Finalmente, comprovou-se que o SBA-15 teve uma taxa de desativação por coque de 1,14 mgcoque gcat-1 h-1, 31 % menor que a taxa do catalisador de alumina, cujos depósitos foram de carbono grafítico bem estruturado e irreversível. Em vista dos resultados obtidos, esta dissertação apresenta as rotas e mecanismos de reação do guaiacol nos catalisadores estudados, conhecimento que é relevante para o desenvolvimento e aprimoramento de futuros catalisadores da HDO. / A key disadvantage of the bio-oils precursors of biodiesel is the high load of oxygenated compounds that reduce their heat of combustion, dropping their efficiency and making them unfeasible on a large scale. In light of that, the hydrodeoxygenation process (HDO) is relevant, since it eliminates these compounds through a catalytic reaction, thus increasing the calorific value of the fuel. In this work, the HDO of guaiacol (2-methoxyphenol) as a model compound of the bio-oils derived from biomass was studied and the performance of Ni-Mo catalysts was evaluated. A catalyst supported on SBA-15 - a high surface area mesoporous silica material - was compared to a traditional gamma-alumina-supported catalyst. For this purpose, a continuous gas phase setup with fixed bed reactor was employed. The catalysts properties were identified by N2 adsorption, SEM, TEM, XRD, H2-TPR, FTIR, O2-TPO, Raman and TGA techniques. Through XRD and TEM, it was verified that smaller and more dispersed NiO and MoO3 particles were formed in the case of the SBA-15 catalyst, due to the lower interaction with the support and the greater surface area, which resulted in a degree of reduction of 91.6% for this catalyst, as opposed to 73.4% for the other one, both analyzed by H2-TPR. The catalytic tests showed that the NiMo/SBA-15 outperforms the alumina catalyst in terms of conversion in the range of 200 to 300 °C, with cyclohexene and cyclohexane as main products, in contrast with major selectivity to catechol and phenol on NiMo/?-Al2O3. At 300 °C, the silica-supported catalyst achieved rates of 66.5% for HDO and 35.3% for HDA (hydrodearomatization), whereas alumina reached only 30.8 and 2.7%, respectively. Finally, it was shown that the SBA-15 catalyst had a coke deactivation rate of 1.14 mgcoke gcat-1 h-1, 31% lower than the alumina catalyst, whose coke deposits consisted of well-structured irreversible graphitic carbon. In view of the results, this dissertation proposes the routes and reaction mechanisms of guaiacol on the studied catalysts, knowledge that is pertinent for the development and improvement of future HDO catalysts.

The pore diameter of a catalyst support controls the diffusion of reactant molecules to the catalytic active sites; thus, affecting the rates and conversions of the hydrotreating reactions. Desirable textural properties of SBA-15 makes it a potential alternative to the conventionally used γ-Al2O3 support due to the fact that its pore size can be manipulated via controlling the synthesis parameters, while maintaining relatively high surface area. Larger pore diameter SBA-15 supports may facilitate the diffusion of bulky molecules as that of the asphaltenes present in the heavy petroleum fractions, making it a potential catalyst support for hydrotreating operations. Considering the very sour nature of Canadas bitumen with high sulfur contents in the range of 2-6 wt %, the appreciably high sulfur contents particularly present in Athabasca derived heavy gas oils (about 4 wt % sulfur), the rising demand for cleaner fuels, and also the increasing stringency on environmental standards, the need for novel and improved hydrotreating catalysts cannot be overemphasized. By varying the molar ratio of hexane to ammonium fluoride, the pore channels of SBA-15 could be varied. Controlling the pore diameter of these supports via micelle swelling facilitated the production of larger pore diameter SBA-15-supported catalysts. In this project, four mesoporous silica SBA-15 catalyst supports with pore diameters in the range of 5-20 nm were synthesized in the preliminary phase using hexane as the micelle swelling agent and subsequently utilized for the loading of 2 wt.% Fe and 15 wt.% W catalyst metals, respectively. The hexagonal mesoscopic structure of these materials were characterized using powder small-angle X-ray scattering (SAXS), N2 adsorption-desorption isotherms, TEM and SEM images. Powder XRD analysis evidenced inhomogeneous metal dispersion on the largest pore diameter catalyst. An optimum pore diameter of 10 nm was found for Cat-B and subsequently used to obtain the optimum Fe and W loadings required to achieve the best hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities. The optimum catalyst was found to be Cat-H with metal loadings of 3 wt.% Fe and 30 wt.% W. At these loadings and temperatures of 375°C, 388°C, and 400°C, HDS activities of 53.4%, 64.1%, and 73.3% with corresponding HDN activities of 21.9%, 26.2%, and 38.3%, respectively, were recorded. Catalytic performance evaluations conducted on equal mass loading using a reference commercial γ-Al2O3-supported FeW catalyst offered HDS activities of 69.3%, 80.4%, and 89.1%, with corresponding HDN activities of 16.4%, 32.4%, and 49.3% at the same temperatures studied. However, no significant changes in HDS and HDN activities were observed for similar evaluations on volume percent metals loading basis. Kinetic studies performed with the optimum FeW/SBA-15 catalyst suggested activation energies of 147.2 and 150.6 kJ/mol for HDS and HDN, respectively, by the Langmuir-Hinshelwoods model. Similar results were predicted by the Power Law and Multi-parameter models for HDS (129.6 and 126.7 kJ/mol, respectively), which does not conclusively make the latter model clearly stand out as the best. Data fitting by the Power Law suggested reaction orders of 2 and 1.5 for HDS and HDN, which seem to be consistent for the hydrotreatment of heavy gas oil. Finally, a long-term deactivation study spanning a period of 60 days time-on-stream showed the optimum catalyst to be stable under hydrotreating experiments conducted in a downward flow micro-trickle bed reactor at temperature, pressure, liquid hourly space velocity (LHSV), and gas/oil ratio of 375400˚C, 8.8 MPa, 1h-1, and 600 mL/mL (at STP), respectively.

The pore diameter of a catalyst support controls the diffusion of reactant molecules to the catalytic active sites; thus, affecting the rates and conversions of the hydrotreating reactions. Desirable textural properties of SBA-15 makes it a potential alternative to the conventionally used γ-Al2O3 support due to the fact that its pore size can be manipulated via controlling the synthesis parameters, while maintaining relatively high surface area. Larger pore diameter SBA-15 supports may facilitate the diffusion of bulky molecules as that of the asphaltenes present in the heavy petroleum fractions, making it a potential catalyst support for hydrotreating operations. Considering the very sour nature of Canadas bitumen with high sulfur contents in the range of 2-6 wt %, the appreciably high sulfur contents particularly present in Athabasca derived heavy gas oils (about 4 wt % sulfur), the rising demand for cleaner fuels, and also the increasing stringency on environmental standards, the need for novel and improved hydrotreating catalysts cannot be overemphasized. By varying the molar ratio of hexane to ammonium fluoride, the pore channels of SBA-15 could be varied. Controlling the pore diameter of these supports via micelle swelling facilitated the production of larger pore diameter SBA-15-supported catalysts. In this project, four mesoporous silica SBA-15 catalyst supports with pore diameters in the range of 5-20 nm were synthesized in the preliminary phase using hexane as the micelle swelling agent and subsequently utilized for the loading of 2 wt.% Fe and 15 wt.% W catalyst metals, respectively. The hexagonal mesoscopic structure of these materials were characterized using powder small-angle X-ray scattering (SAXS), N2 adsorption-desorption isotherms, TEM and SEM images. Powder XRD analysis evidenced inhomogeneous metal dispersion on the largest pore diameter catalyst. An optimum pore diameter of 10 nm was found for Cat-B and subsequently used to obtain the optimum Fe and W loadings required to achieve the best hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) activities. The optimum catalyst was found to be Cat-H with metal loadings of 3 wt.% Fe and 30 wt.% W. At these loadings and temperatures of 375°C, 388°C, and 400°C, HDS activities of 53.4%, 64.1%, and 73.3% with corresponding HDN activities of 21.9%, 26.2%, and 38.3%, respectively, were recorded. Catalytic performance evaluations conducted on equal mass loading using a reference commercial γ-Al2O3-supported FeW catalyst offered HDS activities of 69.3%, 80.4%, and 89.1%, with corresponding HDN activities of 16.4%, 32.4%, and 49.3% at the same temperatures studied. However, no significant changes in HDS and HDN activities were observed for similar evaluations on volume percent metals loading basis. Kinetic studies performed with the optimum FeW/SBA-15 catalyst suggested activation energies of 147.2 and 150.6 kJ/mol for HDS and HDN, respectively, by the Langmuir-Hinshelwoods model. Similar results were predicted by the Power Law and Multi-parameter models for HDS (129.6 and 126.7 kJ/mol, respectively), which does not conclusively make the latter model clearly stand out as the best. Data fitting by the Power Law suggested reaction orders of 2 and 1.5 for HDS and HDN, which seem to be consistent for the hydrotreatment of heavy gas oil. Finally, a long-term deactivation study spanning a period of 60 days time-on-stream showed the optimum catalyst to be stable under hydrotreating experiments conducted in a downward flow micro-trickle bed reactor at temperature, pressure, liquid hourly space velocity (LHSV), and gas/oil ratio of 375400˚C, 8.8 MPa, 1h-1, and 600 mL/mL (at STP), respectively.

Co and Pb are soft oxides, making them useful in partial oxidation catalysis. But it is difficult to prepare high surface area, nanometer size particles due to the low melting point of Pb. In the present study, SBA-15 samples are incorporated with Co and/or Pb at different weight loadings to provide a controlled geometry in nanometer scale via using direct synthesis method. The characterization of the synthesized samples was done by XRD, N2 adsorption isotherms, TEM images and XPS analysis. The increase in the metal loading in SBA-15 causes a decrease in the BET surface area due to the filling of pores with metal atoms. No characteristic peaks of metal oxide was observed up to 15 wt %Pb loading into SBA-15 in the large angle XRD pattern indicating that metal particles are dispersed in the SiO2 structure without accumulating and forming crystals. However, 20 wt%Pb loaded SBA-15 showed more appreciable characteristic peaks, indicating appreciable quantities of crystallites of metal oxide on the surface of silica. The introduction of high amount of cobalt and lead oxides to SBA-15 resulted in the loss of long range order of pores according to the low angle XRD patterns. The hexagonal structure of pores of SBA-15 was v confirmed by TEM images for all samples. XPS analysis indicated that binding energies of O 1s and Si 2p are almost similar in Co or Pb loaded samples, while mixed oxide loaded samples showed slightly higher binding energies which means the structure grows into a different type.

Mesoporous materials attracted great interest due to their huge surface area and adjustable pore sizes. One of the important mesoporous materials is SBA-15 and has larger pore size, hydrothermal stability and thicker walls than other mesoporous materials. In this study, SBA-15 is synthesized by using sol-gel technique and cobalt oxide nanoparticles are incorporated in mesochannels by direct method. SBA-15 was produced from the self-assembly of non-ionic triblock co-polymer (Pluronic 123) and tetra ethyl ortho silicate (TEOS). Then cobalt chloride and cobalt nitrate were added at different loading ratios with two different addition sequences / after polymer and after TEOS. The loading ratios are in Si/Co mols and these ratios are / 15, 10, 5, 3, 1.5, 1 and 0.75 in increasing cobalt amount loaded. Characterization of the produced materials was performed by Powder X-Ray Diffraction (PXRD), Infrared (FTIR) analysis. Nitrogen Phisisorption measurements (BET and BJH Methods) were used to examine the textural properties of produced materials. By means of Transmission Electron Microscopy (TEM) the micro structures of materials were investigated. From the PXRD studies it is observed that the long range order of pores is preserved at even high loading amounts for cobalt chloride addition after TEOS. Co3O4 (JCPDS card no: 42-1467) crystallites are observed for Si/Co mol loading ratios 3, 1.5, 1 and 0.75. Above these loading ratios cobalt oxide is highly dispersed in SBA-15-type structure. FTIR studies revealed the formation of condensed silica network. From the Nitrogen Phisisorption measurements it is observed that addition of cobalt salt decreases the BET surface area of produced materials. All Nitrogen Adsorption-Desorption Isotherms are Type-IV, and has H-1 hysteresis which is a fulfillment of mesoporous structures according to IUPAC classification. BET surface area of samples loaded with cobalt chloride after TEOS possessed higher surface area than other samples. TEM images proved that at loading ratios above 3 there were not any cobalt oxide nanoparticles, cobalt oxide is highly dispersed on silica surface whereas at loading ratios 3 and below there were cobalt oxide nanoparticles embedded in the mesochannels for the samples prepared by addition of cobalt chloride after TEOS.

Methane activation with bromine followed by the condensation of the methyl bromide into higher hydrocarbons or oxygenates is a novel route. However, the selective production of monobrominated methane (CH3Br) at high conversions is a crucial prerequisite. A reaction model was developed according to the kinetic data available in the literature and thoroughly studied to investigate the optimum reactor conditions for selective methane bromination in gas phase. It was concluded that at high methane (&gt / 90%) conversions dibromomethane synthesis was favored at high selectivity (~90%) under the following conditions: T=330 &deg / C, Br:CH4 = 3. Sulfated zirconia included SBA-15 catalysts were prepared and characterized for the catalytic methane activation via bromination. The SBA-15 sol-gel preparation technique was followed and the zirconium was added during the preparation in the form of ZrOCl2&middot / 8H2O with 5-30 mol % ZrO2 with respect to the SiO2 content simultaneously with the silicon source (TEOS). The catalysts were sulfated in 0.25 M H2SO4 solution. The zirconium contents of the catalysts were determined by elemental analysis and 15 wt. % Zr was determined as the highest amount. XRD analysis showed the crystalline zirconia peaks only for high zirconia loadings (&gt / 25 mol % ZrO2) indicating the good distribution of Zr in silica framework at lower loadings. BET surface areas of the sulfated catalysts are in the range of 313-246 m2/g. The porous structures of the catalysts were determined by TEM pictures, which revealed that the increase in Zr content decreased the long range order of pore structure of SBA-15 in agreement with XRD results. The acidities of the catalysts were determined by 1H MAS NMR experiments. Br&oslash / nsted acidity was identified by a sharp 1H MAS NMR line at 10.6 ppm. The highest acidity was observed at 5.2 wt. % Zr loading according to 1H MAS NMR experiments. 29Si MAS NMR analysis showed the formation of Si-O-X linkages (X=H, Zr). Further characterization of Br&oslash / nsted acidity was performed by FT-IR spectroscopy of adsorbed CO at 82 K. The analysis revealed that the Br&oslash / nsted acidity of sulfated catalysts were similar to the acid strength of the conventional sulfated zirconia. In TPD experiments, the basic molecule isopropylamine (IPAm) was adsorbed and decomposition temperature of IPAm was monitored. The temperature decreased from 340 &deg / C to 310 &deg / C in sulfated catalysts, indicating the acidic character of these samples. Catalytic methane bromination reaction tests were performed in a quartz tubular reactor. The results showed that 69% methane conversion was attainable over SZr(25)SBA-15 catalyst at 340 &deg / C. The liquid 1H NMR measurements of the products revealed that &gt / 99% methyl bromide selectivity was achieved.