Synthesis of oleyl oleate as a jojoba oil analog

Synthesis of a wax ester analog of jojoba oil was accomplished from oleic acid and oleyl alcohol with a zeolite as catalyst. A full 2³ factorial design at two levels has been used in the synthesis. The variables selected were temperature, reduced pressure and initial catalyst concentration. The most important variable within the range studied was temperature. Reduced pressure had a negative influence, and initial catalyst concentration showed a positive influence on the process. A response equation has been determined for the yield of ester. The properties of the synthesized product are similar to those of natural jojoba oil.     

Isobutane/2-butene alkylation on MCM-22 catalyst. Influence of zeolite structure and acidity on activity and selectivity

The catalytic behavior of the novel MCM-22 zeolite for the continuous alkylation of isobutane with 2-butene has been investigated at a temperature of 50°C, 2.5 MPa total pressure, and a variety of olefin space velocities. At high olefin conversions the MCM-22 zeolite showed a very high initial cracking activity attributable to strong Brønsted acid sites, as well as to the existence of strong diffusional restrictions of the TMP's (formed inside the zeolite) to exit through the channels. At short times on stream (TOS), TMP's account for ca. 40% of the C₈ fraction. The olefin conversion and the cracking activity rapidly decline with TOS, while the alkylate product became richer in dimethylhexenes, indicating a predominance of 2-butene dimerization and a loss of hydrogen transfer activity as the catalyst aged. Moreover, MCM-22 gives less TMP's than large-pore zeolites (USY, beta, mordenite), but more than the mediumpore ZSM-5 at similar 2-butene conversion. The latter catalyst was much more selective for olefin dimerization than for isobutane alkylation, presumably because formation of the bulkier TMP's was strongly impeded in its smaller pores.     

Synthesis of Pseudoionones by Acid and Base Solid Catalysts

The preparation of pseudoionones by aldol condensation reaction between citral and acetone have been carried out in the presence of acid (HY and beta zeolites), an acid–base (amorphous aluminophosphate) and basic catalysts such as an aluminophosphate oxynitride, MgO and different activated hydrotalcites. The results showed that acid or acid–base catalysts were not successful for performing in one pot the preparation of ionones. MgO and calcined hydrotalcites showed excellent activity and selectivity to pseudoionones, with calcined hydrotalcite more selective than MgO. Moreover, the rate of reaction can be improved by activating the hydrotalcite through rehydration. This activation can be successfully done by simply adding the optimum amount of water to the calcined hydrotalcite before reaction. The inhibiting effect of the concentration citral on the catalytic activity of rehydrated hydrotalcites that has been reported to occur at 273 K can be avoided by working at a reaction temperature of 333 K.     

MCM-41 Heterogenized Chiral Amines as Base Catalysts for Enantioselective Michael Reaction

Cinchonidine and cinchonine have been grafted onto pure silica MCM-41. It has been shown that both supported alkaloids are active catalysts for the Michael addition of ethyl 2-oxocyclopentanecarboxylate and methyl vinyl ketone, anchored cinchonidine being more active and enantioselective than anchored cinchonine. The study of the influence of the polarity of the solvent and reaction temperature on the optical induction shows that there is not a direct correlation between solvent polarity and enantioselectivity, and the maximum optical yield was obtained between 278 and 273 K.     

Kinetics of and catalyst decay accompanying the gas phase rearrangement of cyclohexanone-oxime over a hy ultrastable zeolite

The kinetics of the rearrangement of cyclohexanone-oxime has been studied in a fixed bed, glass tubular reactor at atmospheric pressure and temperatures of 240, 270, 300 and 335°C, using ultrastable HY zeolite catalyst. Several kinetic models, including the Langmuir-Hinshelwood type, have been derived and the best statistical fit has been obtained with a pseudo-first order kinetic equation. The rate constants and activation energies for the formation of the products caprolactam, cyclohexanone and 5-cyanopent-l-ene have been calculated. Based on the evolution of the selectivity with temperature, and the I.R. spectra of the poisoned catalyst, different decay models have been deduced and discussed.     

Hydrocracking of n-heptane. Study of NiO—MoO3 catalysts supported on a HY ultrastable zeolite

The hydrocracking of n-heptane in the temperature range of 573 to 623 K and at 2.45 × 10⁶ Pa pressure has been employed as a test reaction for the study of Ni—Mo bifunctional catalysts supported on a HY ultrastable zeolite. Two groups of catalysts containing 8 and 12 wt% of MoO₃ and different amounts of NiO have been studied. In both series a maximum in the activity has been obtained for catalysts with a Ni/Mo atomic ratio of 0.8-1.0. The order of the impregnation of the oxides can have little influence on the activity. The most active catalyst has been obtained when the zeolite is exchanged with NH⁺₄ ions until the Na⁺ level is less than 2% of the original and calcined at 823 K to obtain a HY ultrastable zeolite. Using this catalyst the rate controlling step could be the transformation of the carbonium ion on the acid sites.     

Zeolites as catalysts in organic reactions. Claisen-Schmidt condensation of acetophenone with benzaldehyde

HY zeolites catalyze the crossed aldol condensation of acetophenone with benzaldehyde, in benzene at 80 °C, to give trans- and cis-chalcones. Together with these expected products, 3,3-diphenylpropiophenone is also produced. In the analogous basic condensation, using phase transfer catalysis, the Michael adduct was not detected, and besides chalcone a small percentage of the Cannizzaro reaction product was observed.     

Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves

The hydrogenation of aromatics, i.e. benzene, toluene, -methylstyrene, anisole, and ethyl benzoate, can be carried out under a very low (1/12000) catalyst to substrate ratio, and mild reaction conditions (80°C, 6 atm of H₂O), on Rh and Ni organometallic complexes anchored on USY zeolites. A strong cooperative effect between the faujasite surface and the transition metal surface complex is thought to be responsible for the simultaneous enhancement of concentrations of arene and H₂ in the neighborhood of the catalytic centers, and for the observed electronic effects.