Effect of the activation procedure on the performance of Mo/H-MFI catalysts for the non-oxidative conversion of methane to aromatics

The effect of pre-treatment on the performance of Mo/H-MFI zeolite catalysts applied to the non-oxidative conversion of methane to aromatics has been investigated. It is demonstrated that catalyst performance depends on activation conditions. Activation of the Mo-oxide/H-MFI precursor with an n-butane/hydrogen mixture results in higher catalyst stability and benzene selectivity which are tentatively attributed to the formation of the -MoC_1−x carbide, with f.c.c. structure as revealed by XRD.     

Unusual selectivity of oxygenate synthesis: Formation of acetic acid from syngas over unpromoted Rh in NaY zeolite

Syngas conversion over Rh/zeolite-NaY catalysts at high-pressure lead to high yields of acetic acid. This unusual selectivity toward one oxygenate in the absence of any catalyst promoter is most pronounced at lower temperature; the apparent activation energy for overall CO-hydrogenation is 23.7 kcal/mol, but for the formation of acetic acid it is 11.9 kcal/mol. The selectivity is little affected by the protons formed during the reduction of Rh. In stiu FT-IR measurement reveals that changes in activity and selectivity during the start-up period are caused by thorough catalyst reconstruction, converting the original Rh⁰ clusters to multinuclear Rh₆(CO)₁₆ and CH₃Rh_y(CO)_x and/or mononuclear CH₃Rh(CO)_x carbonyl complexes, and smaller Rh⁰ clusters. Stable acetate groups, but not the surface bound acetyls, are formed and detected by FT-IR. Most of the cooperating Rh species survive when the pressure is lowered from 1.0 to 0.1 MPa, maintaining a high acetic acid selectivity that is vastly superior to that of the fresh catalyst.     

Design and synthesis of 3D ordered macroporous ZrO2/Zeolite nanocomposites

Zeolite NaY nanocrystals (20−50 nm) were hydrothermally grown on polyelectrolyte-coated three-dimensionally ordered macroporous (3DOM) activated zirconia. The zeolite nanocrystallites uniformly coated the macropore walls of 3DOM sulfated zirconia, but sulfate groups were lost during the hydrothermal reaction. 3DOM tungstated zirconia was found to be more stable in the strong basic environment of the zeolite precursor solution. Further, ion-exchange of zeolite NaY with ruthenium followed by hydrogen-reduction formed a composite of RuNaY and 3DOM activated zirconia. The presence of ruthenium was confirmed by X-ray photoelectron spectroscopy and the external shape of zeolite nanoparticles was maintained after ion-exchange, but the zeolite lattice fringes could not be observed by transmission electron microscopy after incorporation of reduced ruthenium. Although the catalytic activity of the materials has not yet been tested, these hierarchical nano- and microstructures bring multiple catalyst components (modified zeolite Y, a typical Fischer–Tropsch catalyst, and activated zirconia, an isomerization catalyst) together in intimate contact for potential multi-reaction processes.     

Synthesis of zeolites from coal fly ash using mine waters

In this study mine waters obtained from coal mining operations in South Africa were used as a substitute for pure water during the synthesis of zeolites from South African coal fly ash. Procedures that had been optimized to produce single phase zeolite Na-P1 and X using pure water were employed independently. The use of circumneutral mine water resulted in similar quality zeolite Na-P1 and X whereas the use of acidic mine drainage led to the formation of a single phase hydroxysodalite zeolite. Since these two wastes (fly ash and mine waters) are found in close proximity to each other, this study demonstrates that they can be used to ameliorate each other and at the same time produce saleable zeolitic products that can be used to offset their costs of disposal and treatment.     

Theory, spectroscopy and kinetics of zeolite catalysed reactions

The combined use of quantum chemistry and spectroscopy to provide a basis of microkinetics modelling is discussed.     

Selective formation of CH3OH in the photocatalytic reduction of CO2 with H2O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves

Highly dispersed titanium oxide catalysts have been prepared within zeolite cavities as well as in the zeolite framework and utilized as photocatalysts for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH at 328 K. In situ photoluminescence, ESR, diffuse reflectance absorption and XAFS investigations indicate that the titanium oxide species are highly dispersed within the zeolite cavities and framework and exist in tetrahedral coordination. The charge transfer excited state of the highly dispersed titanium oxide species play a significant role in the reduction of CO₂ with H₂O with a high selectivity for the formation of CH₃OH, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity to produce CH₄, being similar to reactions on the powdered TiO₂ catalysts. Ti-mesoporous molecular sieves exhibit high photocatalytic reactivity for the formation of CH₃OH, its reactivity being much higher than the powdered TiO₂ catalysts. The addition of Pt onto the highly dispersed titanium oxide catalysts promotes the charge separation which leads to an increase in the formation of CH₄ in place of CH₃OH formation.     

Microwave-assisted versus conventional synthesis of zeolite A from metakaolinite

This is a comparative study of the synthesis of zeolite A from metakaolinite using both conventional and microwave-assisted heating. The effects of reaction conditions on the rate of formation, crystallinity and actual % yield of zeolite A were investigated. Reaction parameters such as different NaOH molarities (1.0–5.0 M), temperatures (70 and 80 °C), durations (1–8 h) as well as the effect of seeding percentage (1–4%) were tested. The rate of zeolite A formation was found to increase by 2–3 times in microwave treated samples with a notable enhancement in the product crystallinity and % yield whether seeded or un-seeded.     

Preparation and application of zeolite beta with super-low SiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ratio

This paper presents the direct synthesis of super-low SiO₂/Al₂O₃ ratio zeolite beta molecular sieve through a novel route, by which some of aluminium species are added during crystaling process. The IR results show that with the increase of aluminium content in the framework, the frequency of the band in the range of framework vibration (1060–1090 cm⁻¹) shifts to the lower wave-number; the BET surface-area decreases and the basicity of zeolite becomes stronger. In a second step, new adsorbents were obtained by solid-state ion exchanging zeolite beta with Cu(I), Ag(I) cations. The deep-desulfurization (sulfur levels of <1 ppmw) tests were performed using fixed-bed adsorption technique, the sulfur content of the treated and untreated gasoline was analyzed by microcoulometry. The experimental results show that the desulfurization performance of sorbents decreases in order: Cu(I)beta > Ag(I)beta > Na-beta. The best sorbent, Cu(I)beta, has breakthrough adsorption capacities of 0.236 mmolS/g of sorbent for model gasoline.     

Synthesis of pure zeolite Y using soluble silicate, a two-level factorial experimental design

Four methods were used for the synthesis of pure zeolite Y using soluble silicate as a silica source: (1) the gelling of soluble silicate to silica–alumina gel, by aluminate (or aluminium sulphate), (2) the precipitation of soluble silicate to precipitated silica–alumina gel, by aluminate (or aluminium sulphate), (3) the gelling of soluble silicate by sulphuric acid plus alumina impregnation, and (4) the precipitation of soluble silicate by sulphuric acid plus alumina impregnation. A 2⁴ two-level factorial design was used to study the influence of four different variables on the purity of zeolite Y (expressed in terms of degree of crystallinity). The ageing time turned out to be the most significant variable. Synthesis time, alkalinity and mixing rate were also found to be statistically significant. X-ray diffraction patterns were used to characterize the samples, which ranged from well-crystallized faujasite structures to amorphous materials. The highest purity achieved in method (1) was 38%. The best synthesis condition derived from method (1) was applied to the other three methods. Only method (4) yielded the pure zeolite Y. Therefore, the effect of silica–alumina precursor preparation on producing the pure zeolite Y is extremely important.     

Photocatalytic oxidation of aliphatic and aromatic sulfides in the presence of silica adsorbed or zeolite-encapsulated 2,4,6-triphenyl(thia)pyrylium

Solid photocatalysts in which the 2,4,6-triphenylpyrylium (TP) or 2,4,6-triphenylthiapyrylium cation (TTP) are encapsulated within zeolite Y or deposited on mesoporous silica are used as photosensitizers for the oxidation of sulfides, both aromatic and aliphatic, in solvents of various polarity. Contrary to the same cations in solution, these solid sensitizers are not significantly degraded during operation. An effective oxygenation takes place leading to sulfoxides, disulfides, sulfinic and sulfenic esters as well as sulfonic acids. This large scope method shows a limited dependence on the substrate structure and on conditions and is suitable for the abatement of sulfur-containing pollutants.