Resistance to Sulfur and Oxygenated Compounds of Supported Pd, Pt, Rh, Ru Catalysts

Badano, Juan; Quiroga, Mónica; Betti, Carolina; Vera, Carlos Román; Canavese, S.A.; Coloma, Fernando

doi:10.1007/s10562-010-0336-x

Cited by 34 publications

(55 citation statements)

References 38 publications

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“…In previous works we have reported that monometallic Pd catalysts prepared from chlorinated precursors are more active, sulfur and oxygen resistant than similar Pd catalysts prepared from nitrogenated salts or other noble metal catalysts (Pt, Ru and Rh) [6,8]. We have also reported that when Pd is supported over composite organic-inorganic supports, the resulting catalysts prove to be highly active for the selective hydrogenation of styrene [9].…”

Section: Introductionmentioning

confidence: 79%

Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst

Betti

Badano

Lederhos

et al. 2015

Reac Kinet Mech Cat

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This is a study on the kinetics of the liquid-phase hydrogenation of styrene to ethylbenzene over a catalyst of palladium supported on an inorganic-organic composite. This support has a better mechanical resistance than other commercial supports, e.g. alumina, and yields catalysts with egg-shell structure and a very thin active Pd layer. Catalytic tests were carried out in a batch reactor by varying temperature, total pressure and styrene initial concentration between 353-393 K, 10-30 bar, and 0.26-0.60 mol L -1 , respectively. Kinetic models were developed on the assumptions of dissociative hydrogen chemisorption and non-negligible adsorption of hydrogen and styrene. Final chemical reaction expressions useful for reactor design were obtained. The models that best fitted the experimental data were those ones that considered the surface reaction as the limiting step. In this sense a two-step Horiuti-Polanyi working mechanism with half hydrogenation intermediates gave the best fit of the experimental data. The heats of adsorption of styrene and ethylbenzene were also estimated.

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Section: Introductionmentioning

confidence: 79%

Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst

Betti

Badano

Lederhos

et al. 2015

Reac Kinet Mech Cat

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“…These species would have the formula, Pd η+ Cl x O y with 0 < η < 2. 6 The bimetallic PdNiN and NiNPd catalysts had a peak at 333.5 ± 0.3 eV that according to some reports would have a higher availability of electrons, i.e. they would be species Pd δ-(with δ < 0).…”

Section: Catalysts Characterizationmentioning

confidence: 96%

“…6 As seen in Table 3 , Lewis acid sites). Besides the lower thioresistance of PdNiN and NiNPd would be related to the amount of exposed Pd δ-species (Lewis basic sites) that promote a strong adsorption of the poison and thus an increase of the blocking of active sties.…”

Section: Catalytic Testmentioning

confidence: 99%

“…Particularly thiophene would interact with the metal surface in a planar way through the electrons of the aromatic ring (weak η 5 bond). 6,7,34 In the case of the test reactions with thiophene some of the d electrons of Pd would be shared with sulfur atoms, thus decreasing the activity of the catalysts.…”

Section: Catalytic Testmentioning

confidence: 99%

“…In a previous work with monomethalic catalysts the effect of chlorine for the sulfurresistance was studied. In Badano et al, 6 it was found that chloride complex species (Pd x δ+ O y Cl z and the Pt x δ+ O y Cl z , with δ < 2) present in the surface could hinder the adsorption of poisons via a steric factor (big size of chlorine ligands) or an electronic one (high electronegativity). Besides, bimetallic catalysts are potentially thioresistant systems.…”

Section: Introductionmentioning

confidence: 99%

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MORE ACTIVE AND SULFUR RESISTANT BIMETALLIC Pd-NI CATALYSTS

Betti¹,

Carrara²,

Badano³

et al. 2017

Quim. Nova

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The influence of the kind of metal precursor and the sequence of impregnation on the properties of Pd-Ni catalysts was evaluated during the test reaction of selective hydrogenation of styrene to ethylbenzene by means of physicochemical characterization. The focus was put on the final hydrogenating activity and the resistance to deactivation by sulfided compounds (thiophene). The used techniques of characterization were ICP, XPS, XDR, TPR, CO chemisorption and TEM. XPS results indicated the presence of different Pd species: Pd δ-, Pd 0 and Pd δ+ . In the case of the Ni containing catalysts, Ni 0 and NiO species were also detected. These palladium and nickel species would be responsables of the variation of activity and sulfurresistance of the catalysts. NiClPd catalysts had a higher resistance to deactivation by sulfur poisoning. This was associated to a higher concentration of Pd η+ Cl x O y species that would prevent the adsorption of thiophene by both steric and electronic effects. It could also be due to the lower concentration of Pd 0 and Ni 0 on these catalysts, as compared to those shown by the PdNiCl catalysts. Both the Pd 0 and Ni 0 species are more prone to poisoning because of their higher electronic availability.

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Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

Cordoba

Betti

Bovier

et al. 2021

J of Chemical Tech & Biotech

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BACKGROUND: Pd nanoparticles over different supports were evaluated during the alkyne selective hydrogenation of medium chain (C 7 and C 5 ) and the 1-pentene purification at mild operational conditions (150 kPa and 303 K). The role of support and chloride was investigated; γ-Al 2 O 3 , γ-Al 2 O 3 modified with Mg, CaCO 3 and activated carbon were used as supports, and PdCl 2 as precursor salt. The classical Lindlar catalyst was used as reference.RESULTS: Surface acidity of supports, active sites dispersion and surface species (MgO, Pd x Cl y O z and/or functional groups) can favor or disfavor the desorption of 1-alkene during the purification of 1-pentene stream. The smallest particle sizes (3.8-10.0 nm) favor the dissociative adsorption of hydrogen over Pd°active sites, promoting good catalytic behavior. The best synthesized catalysts are Pd/Al-Mg and Pd/Ca, and their high selectivity (≥90%) is favored by the presence of superficial acidic Lewis sites. On the contrary, lower selectivity (74-80%) is assessed on catalysts with Brönsted acidic sites (Pd/Al and Pd/RX3) that favored the undesired overhydrogenation or isomerization reactions. CONCLUSION:The geometric and electronic properties of the support have a major influence on the activity and selectivity of the catalysts. Low loaded Pd catalysts supported on Al 2 O 3 -Mg and CaCO 3 (Pd/Al-Mg, Pd/Ca) can be used for the purification of medium or large terminal alkenes at mild reaction conditions as an alternative to the toxic Lindlar commercial catalyst.

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Resistance to Sulfur and Oxygenated Compounds of Supported Pd, Pt, Rh, Ru Catalysts

Cited by 34 publications

References 38 publications

Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst

Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst

MORE ACTIVE AND SULFUR RESISTANT BIMETALLIC Pd-NI CATALYSTS

Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

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