Search results for "Product distribution"
showing 10 items of 13 documents
Selective Introduction of Acid Sites in Different Confined Positions in ZSM-5 and Its Catalytic Implications
2018
Controlling the location of acid sites in zeolites can have a great effect on catalysis. In this work we face the objective of directing the location of Al into the 10R channels of ZSM-5 by taking advantage of the structural preference of B to occupy certain positions at the channel intersections, as suggested by theoretical calculations. The synthesis of B-Al-ZSM-5 zeolites with variable Si/Al and Si/B ratios, followed by B removal in a postsynthesis treatment, produces ZSM-5 samples enriched in Al occupying positions at 10R channels. The location of the acid sites is determined on the basis of the product distribution of 1-hexene cracking as a test reaction. The higher selectivity to prop…
Cracking of n-heptane on a hzsm-5 zeolite. The influence of acidity and pore structure
1985
Abstract The crackino of n-heptane on a HZSM-5 zeolite has been studied in a continuous qlass flow reactor, at atmospheric pressure, up to 470°C. The initial selectivities to the different reaction products, kinetic rate constants, activation energies and decay parameters have been calculated and compared with those obtained using a large pore zeolite (HYUS). A different product distribution is obtained with the two zeolites. In that way, and considering initial selectivities, different C 6 /C 1 , C 5 /C 2 , C 4 /C3, i-C 4 /n-C 4 , ethylene/ethane, propylene/propane ratios have been found on the two zeolite catalysts. The results have been quantitatively explained by considerinq a direct cr…
Current views on the mechanism of catalytic cracking
2000
Abstract The cracking mechanisms of hydrocarbons have been reviewed and the kinetic and thermodynamic implications of the different steps, i.e. initiation, chain propagation, and termination, have been discussed. Although the cracking mechanism of olefins and alkylaromatics is well established, the initiation step for the cracking of paraffins is still under debate. The role of Bronsted-type active sites and also the possible influence of extra-framework Al species in the case of zeolite catalysts, especially when commercial feeds and industrial conditions are employed, are presented. The product distribution is determined by the number of propagation events occurring per initiation step, a…
Epoxidation of stilbene using supported gold nanoparticles: cumyl peroxyl radical activation at the gold nanoparticle surface.
2014
The catalytic epoxidation of cis-stilbene using cumene as a solvent in the presence of supported gold nanoparticles (AuNP) yields a mixture of cis and trans-stilbene oxides. EPR and product distribution studies support a new mechanistic proposal where oxygen centred radicals activate the AuNP surface and form active surface oxygen species responsible for the epoxidation products.
Cracking behavior of zeolites with connected 12- and 10-member ring channels: The influence of pore structure on product distribution
1997
n-Heptane has been cracked on a CIT-1 zeolite which has connected 12- and 10-member ring (MR) channels, and its behavior was compared with that of MCM-22 with nonconnected 12- and 10-MR channels, and SSZ-24 and BETA with unidirectional and tridirectional 12-MR channels, respectively. The kinetic rate constant is highest for CIT-1, and the decay constant is lowest. From the selectivity point of view, its behavior can be better represented by a system with large cavities (the intersections between the 12- and 10-MR) connected by windows. This gives a behavior typical of that of large pore zeolites. CIT-1 produces a remarkably high selectivity toi-C4, and specially to isobutane. This zeolite s…
Sunlight-induced functionalisation reactions of heteroaromatic bases with aldehydes in the presence of TiO2: A hypothesis on the mechanism
2007
In previous studies we reported a new photocatalytic system involving polycrystalline TiO2 for the selective functionalisation of heteroaromatic bases with ethers and amides. In order to extend the applications of this new reaction and to better understand the mechanism involved, we have examined aromatic and aliphatic aldehydes as acyl radical sources for the nucleophilic addition to protonated N-heteroarenes in acetonitrile as the solvent and TiO2/H2O2 as the photocatalytic system. Acyl radicals may undergo decarbonylation to yield the corresponding alkyl radicals. Acyl/alkyl derivative ratios depend on the nature of the aldehydes, and present a different distribution from that obtained i…
Selective oxidation of phenol and benzoic acid in water via home-prepared TiO2 photocatalysts: Distribution of hydroxylation products
2012
Abstract The hydroxylation of phenol (a substrate containing an electron donor group) and of benzoic acid (a substrate containing an electron withdrawing group) has been carried out by the photocatalytic method in aqueous suspensions containing commercial or home prepared TiO2 samples. The aim of the work was to study the distribution of hydroxylation products when different photocatalysts were used and to correlate the selectivity to some physico-chemical features of the powders. The samples were characterized by X-ray diffraction, thermogravimetry, determination of crystalline phase percentage, specific surface area and zero charge point. The photoreactivity results indicate that the prod…
Reactions of dirhodium(II) monometallated compounds with phosphines. Factors affecting the reactivity and the structure of the doubly-metallated comp…
1992
Abstract Monometallated compounds of formula Rh2(O2CCH3)3[(p-XC6H3)P(p-XC6H4)2](HO2CCH3)2 (X=CH3, Cl) have been prepared in good yield. The reactions with p-substituted triarylphosphines P(p-X′C6H4)3 (X′=CH3, H, Cl) have been studied. For X=X′ and [P]/[Rh2]=1 all the resulting doubly metallated compounds Rh2(O2CCH3)2[(p- XC6H3)P(p-XC6H4)2](HO2CCH3)2 (X=CH3, Cl) have head-to-tail (H-T) structure. For [P]/[Rh2]=3 reaction progress is observed at room temperature. When X=X′ a 1:1 mixture of H-T and H-H compounds is formed for X=Cl but only the H-H compound is obtained for X=CH3. For X ≠ X′ mixtures of H-T and H-H compounds are obtained. The entering phosphine, and to a less extent the phosphin…
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…