The effect of chromium on sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

Sulfur is a major poison to noble metal catalysts for deep aromatic hydrogenation in the petroleum refining industry. In order to study the sulfur resistance of Pd-based catalysts, a series of Pd, Cr, and PdCr catalysts supported on HY-Al2O3 were studied by NH3-TPD, pyridine-adsorption IR, TPR, IR spectra of adsorbed CO, and toluene hydrogenation in the presence of 3000 ppm sulfur as thiophene under the following conditions: 533-573 K, 4.2 MPa, and WHSV 4.0 h(-1). Cr has no influence on the acidity of the catalysts. TPR patterns and in situ IR spectra of adsorbed CO revealed a strong interaction between Cr and Pd, and the frequency shift of linear bonded CO on Pd indicates that the electron density of Pd decreases with the increase of the Cr/Pd atomic ratio. The catalytic performance of Pd, Cr, and PdCr catalysts shows that the sulfur resistance of Pd is strongly enhanced by Cr, and the activity reaches its maximum when the Cr/Pd atomic ratio equals 8. The active phase model "Pd particles decorated by Cr2O3" is postulated to explain the behavior of PdCr catalysts. (C) 2001 Academic Press.

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.