Search results for "ZEOLITE"
showing 10 items of 203 documents
A Multisite Molecular Mechanism for Baeyer-Villiger Oxidations on Solid Catalysts Using Environmentally Friendly H2O2 as Oxidant
2005
The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO 2 (rutile). The tin active site has been modeled by means of a S…
Net charge and polarizability of zeolitic Brønsted acidic sites
2007
The interacting induced-dipoles polarization model, implemented in our program POLAR, is used for the calculation of the effective polarizability of the zeolitic bridged OH group, which results much higher than that of the free silanol group. A high polarizability is also calculated for the bridged OH group with a Si4+, in the absence of Lewis-acid promotion of silanol by Al3+. The crystal polarizability is estimated from the Clausius-Mossotti relationship. Siliceous zeolites are low-permittivity isolators. The interaction of a weak base with the zeolitic OH can be considered as a local bond. Only when cations are located in the zeolite micropore, next to tetrahedra that contain trivalent c…
Cluster and Periodic Calculations of the Ethene Protonation Reaction Catalyzed by theta-1 Zeolite: Influence of Method, Model Size, and Structural Co…
2001
The protonation of ethene by three different acid sites of theta-1 zeolite was theoretically studied to analyze the extent and relevance of the following aspects of heterogeneous catalysis: the local geometry of the Bronsted acid site in a particular zeolite, the size of the cluster used to model the catalyst, the degree of geometry relaxation around the active site, and the effects related to medium- and long-range interactions between the reaction site and its environment. It has been found that while the reaction energy is very sensitive to the local geometry of the site, the activation energy is mainly affected by the methodology used and by electrostatic effects on account of the carbo…
Cracking Activity and Hydrothermal Stability of MCM-41 and Its Comparison with Amorphous Silica-Alumina and a USY Zeolite
1996
It has been found that the cracking activity of MCM-41 for a reaction catalyzed by strong acids site, such asn-heptane cracking, is much lower than that of a USY zeolite, and similar to that of amorphous silica-alumina. The higher activity of USY is due to the presence of stronger Bronsted acid sites in the zeolite. In the case of gas oil cracking, the greater accessibility of the large molecules to acid sites in MCM-41 relative to USY makes the difference in activity between these two catalysts much smaller than for the pure hydrocarbon. In the calcined state MCM-41 is more active and gives more gasoline and less gases and coke than amorphous silica-alumina. However, when the catalysts wer…
Hemicellulose hydrolysis catalysed by solid acids
2013
Depolymerising hemicellulose into platform sugar molecules is a key step in developing the concept of an integrated biorefinery. This reaction is traditionally catalysed by either enzymes or homogeneous mineral acids. We compared various solid catalysts for hemicellulose hydrolysis, running reactions in water, under neutral pH and relatively mild temperature and pressure (120°C and 10 bar) conditions. Sulphonated resins are highly active, but they leach out sulphonic groups. Sulphonated silicas are less active, but more stable. They have weakly and strongly bound sites and the strongly bound ones do not leach. Zeolites are moderately active and stable. Among them, H-ferrierite especially, d…
Influence of the process variables on the product distribution and catalyst decay during cracking of paraffins
1986
Abstract The influence of the partial pressure of the hydrocarbon, reaction temperature, time on stream and the presence of olefins on the product distribution and the kinetics and decay during the cracking of n-heptane on an REHY zeolite were studied. It was found that the isomerization to cracking ratio depends on the hydrocarbon partial pressure. The active sites for cracking and isomerization are not the same and those for cracking decay faster, the selectivity changing with the degree of decay of the zeolite. The protolytic to β-cracking ratio, and therefore the paraffin to olefin ratio, are a function of the partial pressure of n-heptane. Both reactants and products have a marked infl…
The influence of branching isomerization on the product distribution obtained during cracking of n-heptane on acidic zeolites
1985
Abstract The initial selectivities for the primary products occurring during the cracking of n-heptane on a rare-earth (RE)-HY ultrastable zeolite up to 470°C have been calculated. The activation energies for the cracking of n-heptane and its branched isomers in the fraction C4 + C3 have been obtained by molecular orbital calculations, and these values and the predicted product distribution have been compared with those obtained experimentally. It is concluded that the cracking of n-heptane on large-pore zeolites may take place by different parallel routes involving protolytic and β-cracking of n-heptane and β-cracking of the readily formed branched carbenium ions. The relative importance o…
Adsorption of chlorinated volatile organic compounds on hydrophobic faujasite: correlation between the thermodynamic and kinetic properties and the p…
1998
This work deals with a thermodynamic and kinetic study of the adsorption of single volatile organic compounds (VOCs) (dichloromethane (DCM), 1,2-dichloroethane (DCA), trichloroethene (TCE) and tetrachloroethene (PCE)) on a dealuminated faujasite Y by simultaneous measurements of the adsorbed amounts, adsorption heats and diffusivities. The type V isotherms and the weak values of derivative enthalpies allowed us to predict that the competitive adsorption of their mixture would be similar to a distillation. This prediction was verified experimentally: the breakthrough curves of VOC mixtures showed that the adsorbate with the higher boiling point displaced the adsorbate with the lower boiling …
Catalytic Performance of the New Delaminated ITQ-2 Zeolite for Mild Hydrocracking and Aromatic Hydrogenation Processes
2001
Abstract Catalysts based on NiMo and Pt supported on the new delaminated ITQ-2 zeolite have been prepared and their catalytic properties evaluated for the mild hydrocracking (MHC) of vacuum gasoil and aromatic hydrogenation. The results were compared with those obtained using other conventional supports, e.g., silica, γ-alumina, amorphous silica–alumina (25 wt% Al 2 O 3 ), and USY zeolite, all of which contain the same metal loading as the ITQ-2 material. In the case of MHC of vacuum gasoil, NiMo/ITQ-2 displayed a higher hydrocracking activity than NiMo/SiO 2 –Al 2 O 3 and NiMoγ-Al 2 O 3 , and even higher activity than NiMo/USY in the range 375–425°C. Moreover, NiMo/ITQ-2 had a selectivity …
Adsorption of gaseous p-xylene and m-xylene on NaY, KY, and BaY zeolites: Part 1. Adsorption equilibria of pure xylenes
1995
Abstract Isothermal and isobaric adsorptions of p -xylene and m -xylene on NaY, KY, and BaY are studied by thermogravimetry between 25°C and 400°C, and 10 Pa and 1014 Pa. At low filling BaY shows a stronger affinity for xylenes than the other zeolites. At high temperature and low pressure its adsorption capacity is greater than those of NaY and KY. These two zeolites have a similar behavior and adsorb more m -xylene than p -xylene. At low temperature and high pressure KY adsorbs p -xylene like NaY and m -xylene like BaY, and, unlike NaY, the adsorption capacities of KY and BaY are higher for p -xylene than for m -xylene. The substitution of K + or Ba 2+ for Na + decreases the adsorption cap…