Effect of Fe Additives on the Catalytic Performance of Ion-Exchanged CsX Zeolites for Side-Chain Alkylation of Toluene with Methanol

The side-chain alkylation of toluene with methanol was investigated over some Fe-modified Cs ion-exchanged X zeolite (CsX) catalysts prepared via the impregnation method using different iron sources. The absorption/activation behaviors of the reactants on the surface of the catalysts were studied by in situ Fourier-transform infrared (FT-IR) spectroscopy and temperature programmed desorption (TPD) mass measurements. Modification of CsX with a small amount of FeCl3 could result in a considerable decrease in catalytic activity, due mainly to the remarkable decrease in the density of acidic and basic sites of the catalysts. Interestingly, the Fe(NO3)(3)-modified CsX with an optimum Fe loading of 0.15 wt.% shows improved catalytic activity and high yield compared to the side-chain alkylation products. Modification of CsX with Fe(NO3)(3) could also result in a decrease in basic sites of the catalyst. However, such a change does not bring an obvious negative effect on the adsorption/activation of toluene, while it could effectively inhibit the generation of the undesired bidentate formate. Furthermore, the introduced FeOx species (derived from the decomposition of Fe(NO3)(3)) may also act as new Lewis acidic sites to participate in the activation of methanol and to stabilize the formed active intermediates (i.e., unidentate formate). Therefore, modification of CsX with a suitable amount of Fe(NO3)(3) may adjust its adsorption/activation ability for reagents by changing the acid-base properties of the catalyst, which can finally enhance the catalytic performance for the side-chain alkylation of toluene with methanol.