Carolina Betti

Sulfur Resistance of Pt-W Catalysts

The sulfur resistance of low-loaded monometallic Pt catalysts and bimetallic Pt-W catalysts during the partial selective hydrogenation of styrene, a model compound of Pygas streams, was studied. The effect of metal impregnation sequence on the activity and selectivity was also evaluated. Catalysts were characterized by ICP, TPR, XRD, and XPS techniques. Catalytic tests with sulfur-free and sulfur-doped feeds were performed. All catalysts showed high selectivities (>98%) to ethylbenzene. Activity differences between the catalysts were mainly attributed to electronic effects due to the presence of different electron-rich species of Pt0 and electron-deficient species of . Pt0 promotes the cleavage of H2 while the adsorption of styrene. The catalyst successively impregnated with W and Pt (WPt/Al) was more active and sulfur resistant than the catalyst prepared with an inverse impregnation order (PtW/Al). The higher poison resistance of WPt/Al was attributed to both steric and electronic effects.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 oC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

NANOPARTICLES OF TUNGSTEN AS LOW-COST MONOMETALLIC CATALYST FOR SELECTIVE HYDROGENATION OF 3-HEXYNE

to be active and stereoselective for the production of (Z)-3-hexene, had the following order: 7.1WN/A > 8.5 WN/A ≥ 4.5 WN/A. Additionally, the performance of the synthesized xWN/A catalysts exhibited high sensitivity to temperature variation. In all cases, the maximum 3-hexyne total conversion and selectivity was achieved at 323 K. The performance of the catalysts was considered to be a consequence of two phenomena: a) the electronic effects, related to the high charge of W (+6), causing an intensive dipole moment in the hydrogen molecule (van der Waals forces) and leading to heterolytic bond rupture; the H+ and H- species generated approach a 3-hexyne adsorbate molecule and cause heterolytic rupture of the C≡C bond into C- = C+; and b) steric effects related to the high concentration of WO3 on 8.5WN/A that block the Al2O3 support. Catalyst deactivation was detected, starting at about 50 min of reaction time. Electrodeficient W 6+ species are responsible for the formation of green oil at the surface level, blocking pores and active sites of the catalyst, particularly at low reaction temperatures (293 and 303 K). The resulting best catalyst, 7.1WN/A, has low fabrication cost and high selectivity for (Z)-3-hexene (94%) at 323 K. This selectivity is comparable to that of the classical and more expensive industrial Lindlar catalyst (5 wt% Pd). The alumina supported tungsten catalysts are low-cost potential replacements for the Lindlar industrial catalyst. These catalysts could also be used for preparing bimetallic W-Pd catalysts for selective hydrogenation of terminal and non-terminal alkynes.

Kinetic Study of the Partial Hydrogenation of 1-Heptyne over Ni and Pd Supported on Alumina

© 2012 Maccarrone et al., licensee InTech. This is an open access chapter distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. Kinetic Study of the Partial Hydrogenation of 1-Heptyne over Ni and Pd Supported on Alumina

High-Active Metallic-Activated Carbon Catalysts for Selective Hydrogenation

A series of low-loaded metallic-activated carbon catalysts were evaluated during the selective hydrogenation of a medium-chain alkyne under mild conditions. The catalysts and support were characterized by ICP, hydrogen chemisorption, Raman spectroscopy, temperature-programmed desorption (TPD), temperature-programmed reduction (TPR), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR micro-ATR), transmission electronic microscopy (TEM), and X-ray photoelectronic spectroscopy (XPS). When studying the effect of the metallic phase, the catalysts were active and selective to the alkene synthesis. NiCl/C was the most active and selective catalytic system. Besides, when the precursor salt was evaluated, PdN/C was more active and selective than PdCl/C. Meanwhile, alkyne is present in the reaction media, and geometrical and electronic effects favor alkene desorption and so avoid their overhydrogenation to the alkane. Under mild conditions, nickel catalysts are considerably more active and selective than the Lindlar catalyst.

New Strategies for Obtaining Inorganic-Organic Composite Catalysts for Selective Hydrogenation

Pd/composites are catalysts in which the catalytically active metal phase is located in a small layer on the support surface. The metal distribution obtained on these supports corresponds to a structure commonly known as “egg-shell”. This distribution is optimal for reactions that have heat or mass transfer resistances. The small thickness of the metal layer is mainly attributed to the use of support pellets of mixed organic–inorganic composition, the special interaction between the hydrophobic–hydrophillic support surface and the metal species (Pd or Pt) present in the impregnating aqueous solution. Pd/composite catalysts are active and selective for the reactions of selective hydrogenation of styrene, 1-heptyne, 3-hexyne and 2,3-butanone, and enantioselective hydrogenation of ethyl pyruvate. These reactions are of interest in both academic and industrial aspects.

Alkyne Selective Hydrogenation with Mono- and Bimetallic- Anchored Catalysts

Partial hydrogenation of alkynes has industrial and academic relevance on a large scale; industries such as petrochemical, pharmacological and agrochemical use these compounds as raw material. Finding an economic, active and selective catalyst for the production of alkenes through partial hydrogenation of alkynes is thus an important challenge. Monoand bimetallic catalysts (palladium, ruthenium and nickel) were synthetized by the incipient wetness technique using gamma alumina and an activated carbon as supports. The catalysts were characterized by inductively coupled plasma, hydrogen chemisorption, temperature-programmed reduction and X-ray photoelectronic spectroscopy (XPS). The objective of this work is to study 1-heptyne-selective hydrogenation using supported catalysts influenced by different factors: (a) pretreatment reduction temperature, (b) reaction temperature, (c) type of support, (d) metal loading, (e) precursor salt and (f) addition of a second metal to monometallic palladium catalyst. The Lindlar commercial catalyst, commonly used in these types of reactions, was used for comparative purposes. XPS technique allowed verifying that the presence of electron-deficient species on the catalyst surface with high metal loading affects the conversion and selectivity to the desired product. Nevertheless, the influence of geometrical effects and/or mixed active sites in the catalysts, as well as metal-metal and metal-support interactions, cannot be neglected.