Deactivation study of Ru-Sn-B/Al2O3 catalysts during selective hydrogenation of methyl oleate to fatty alcohol

In this work, the deactivation of the Ru-Sn-B/Al2O3 catalyst prepared by the incipient wetness method in the selective hydrogenation reaction of methyl oleate to fatty alcohol was studied. There was a decrease in both the activity and selectivity of fatty alcohol during successive reaction experiments. The fresh and deactivated catalysts were evaluated by different techniques such as TPR, XPS, TGA, Raman, and FTIR to determine the deactivation causes. Lower Ru and Sn content were found in the deactivated catalyst due to the loss of the active material during hydrogenation reaction. As the metal loss was more important for Ru than for Sn, the Ru/Sn ratio was changed, leading to a decrease of the selectivity. Moreover, the analysis of the XPS peak by the deconvolution of Sn species suggests the more active (SnOx) species for selective hydrogenation are more affected than the less selective (SnOy). Coke deposition was not observed by Raman and FTIR.Fil: Sánchez, María A.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Vicerich, Maria Ana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Gioria, Esteban Gaston. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Gutierrez, Laura Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Adsorptive properties of silica gel for biodiesel refining

The refining of biodiesel by adsorption over silica gel was assessed. Silica gel samples were used for the adsorption of glycerol and monoglycerides. Room-temperature isotherms for the adsorption of glycerol were measured for biodiesel samples contaning only fatty acid methyl esters or samples spiked with contaminants, such as water, methanol, monoglycerides, and soaps. The results indicate that adsorption of glycerol and monoglycerides contained in biodiesel over silica is very efficient and robust. Adsorption of glycerol is not influenced by the presence of small amounts of water arid soaps. The presence of monoglycerides lowers the adsorption capacity of glycerol because of the competition of monoglycerides for the same adsorption sites. Methanol adversely affects the adsorption in a different way. It increases the activity of glycerol in the liquid phase and reduces the adsorption affinity and adsorption capacity of silica. Conventional biodiesel refining downstream transesterification reactors currently performed by decanting/washing or centrifugation/washing can be conveniently replaced by simple decanting and silica adsorption, thus preventing the issue of excessive amount of effluent waters.Fil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Yori, Juan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Adsorptive properties of silica gel for biodiesel refining

The refining of biodiesel by adsorption over silica gel was assessed. Silica gel samples were used for the adsorption of glycerol and monoglycerides. Room-temperature isotherms for the adsorption of glycerol were measured for biodiesel samples contaning only fatty acid methyl esters or samples spiked with contaminants, such as water, methanol, monoglycerides, and soaps. The results indicate that adsorption of glycerol and monoglycerides contained in biodiesel over silica is very efficient and robust. Adsorption of glycerol is not influenced by the presence of small amounts of water arid soaps. The presence of monoglycerides lowers the adsorption capacity of glycerol because of the competition of monoglycerides for the same adsorption sites. Methanol adversely affects the adsorption in a different way. It increases the activity of glycerol in the liquid phase and reduces the adsorption affinity and adsorption capacity of silica. Conventional biodiesel refining downstream transesterification reactors currently performed by decanting/washing or centrifugation/washing can be conveniently replaced by simple decanting and silica adsorption, thus preventing the issue of excessive amount of effluent waters.Fil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Yori, Juan Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Influence of methanol addition during selective hydrogenation of benzene to cyclohexene

The addition of a certain methanol concentration during benzene hydrogenation on Ru/Al2O3 improves the selectivity to cyclohexene because of a preferential adsorption of methanol on the most active Ru sites.Fil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: L'argentiere, Pablo Cesar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Figoli, Nora Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Effect of the support on the selective hydrogenation of benzeneover ruthenium catalysts. 1. Al2O3 and SiO2

The effect of the support on the liquid phase selective hydrogenation of benzene to cyclohexene over Ru catalysts was studied. Catalysts were prepared using RuCl3 as precursor and characterized by hydrogen chemisorption, XPS and TPR. The reaction was carried out at 373 K and 2 MPa using a stirred tank reactor. It was found that the catalytic activity is not influenced by the Ru dispersion. More electron-deficient Ru species are present on Al 2O3 than on SiO2. The electronic state of Ru affects the selectivity to cyclohexene.Fil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Fígoli, Nora. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Pascual, Fernando-Coloma. Universidad de Alicante; EspañaFil: L'Argentière, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Influence of the operating conditions and kinetic analysis of the selective hydrogenation of oleic acid on Ru-Sn-B/Al2O3 catalysts

International audienceThe influence of the operating conditions on the selectivity and activity of Ru-Sn-B/Al2O3 catalysts for the hydrogenation of oleic acid to oleyl alcohol was studied. It was found that the Ru-Sn-B/Al2O3 catalyst is selective to oleyl alcohol while Ru or Ru-B/Al2O3 catalysts are not selective to produce oleyl alcohol. The electronic and catalytic properties of Ru are modified by the strong interaction between Sn and B. The incorporation of Sn leads to catalysts capable of producing oleyl alcohol. The experiments of oleic acid hydrogenation showed that an increase in reaction temperature leads to an increase in activity while the selectivity to oleyl alcohol goes through a maximum. This is because the reactions of hydrogenation of C=C double bond have lower activation energies than hydrogenolytic reactions. The increase in operating pressure has a positive effect on conversion and a more important effect on selectivity. A very simple first order kinetic model is proposed and reasonably represents the results obtained. This model can be useful to compare catalyst performance more rationally

Effect of the method of addition of Ge on the catalytic properties of Pt-Re/Al2O3 and Pt-Ir/Al2O3 naphtha reforming catalysts

Pt-Re/Al2O3 and Pt-Ir/Al2O3 catalysts were modified by addition of an inactive metal, germanium, in order to suppress the strong hydrogenolytic activity of these types of catalysts. The influence of the addition method of germanium over Pt-Re and Pt-Ir catalysts was studied in order to find which one (catalytic reduction, successive impregnations and coimpregnation methods were used) produced the best trimetallic catalysts in terms of activity, selectivity and passivation of the hydrogenolytic activity of the metal function of the parent bimetallic catalyst. Ge addition produces a significant decrease of the activity of the metal function, affecting both non-demanding and demanding reactions and also the methane production during n-heptane reforming. It also produces an inhibition of the acid function but the resulting acid/metal activity ratio is higher than that of the bimetallic parent catalysts. Catalytic reduction was found to be the best method of Ge addition in the case of the Pt-Ir catalyst series, producing the most stable catalysts, with the lowest cracking and the highest toluene yield. The same was true for the Pt-Re catalysts prepared by coimpregnation.Fil: Boutzeloit, Marieme. Université de Poitiers; FranciaFil: Benitez, Viviana Monica. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Especel, Catherine. Université de Poitiers; FranciaFil: Epron, Florence. Université de Poitiers; FranciaFil: Vera, Carlos Roman. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Marécot, Patrice. Université de Poitiers; Franci

Influence of Ge content on the activity of Ru-Ge-B/Al2O 3 catalysts for selective hydrogenation of methyl oleate to oleyl alcohol

The influence of Ge content on the activity and selectivity of Ru-Ge-B/Al2O3 catalysts for the hydrogenation of methyl oleate to oleyl alcohol was studied. The results of catalyst characterization by TPR and XPS show that Ge is deposited on both the metal function aggregates and on the support surface. The fraction of Ge deposited on the metal function is in strong interaction with Ru, so that its metallic activity is significantly modified. Both dehydrogenating and hydrogenolytic activities of Ru are strongly diminished by Ge addition. The Ge/Ru = 2 is the optimum ratio for oleyl alcohol production.Fil: Sánchez, María Amparo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Mazzieri, Vanina Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; ArgentinaFil: Oportus, Marcelo. Universidad de Concepción; ChileFil: Reyes, Patricio. Universidad de Concepción; ChileFil: Pieck, Carlos Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentin

Ru-Sn-B/TiO 2 catalysts for methyl oleate selective hydrogenation. Influence of the preparation method and the chlorine content

International audienceBACKGROUND: Fatty alcohols are produced commercially by selective hydrogenation of fatty acid esters using copper‐chromium catalysts. To reduce drastic reaction conditions, ruthenium‐tin (Ru‐Sn) catalysts reduced with sodium borohydride (NaBH4) have been proposed. Chlorine (Cl) negatively affects the selectivity and activity of this catalytic system. To get further information on why Cl influences the selectivity negatively, this study investigated the influence of the preparation method on titania (TiO2)‐supported catalysts, which leads to catalysts with different Cl contents.RESULTS: The activity and selectivity were greatly affected by the Cl content, which depends on the metal impregnation method (co‐impregnation in excess of solution or co‐impregnation by incipient wetness) and the support pre‐calcination. Chlorine affects the Ru–Sn metal interaction, modifying the activity and selectivity. Catalysts with high Ru–Sn interaction are more selective to oleyl alcohol. Catalysts prepared by the co‐impregnation method exhibit bigger particles than catalysts prepared by the incipient wetness method, with agglomerated Ru3Sn7 cubic phase of 50 nm surrounded by amorphous Ru‐Sn.CONCLUSION: High interaction between Ru and Sn is preferred because segregated Ru species are not selective for the formation of oleyl alcohol. The electronic state of Ru0 is very important because small variations in the electron density lead to a decrease in the adsorption of hydrogen, or because Ru0‐H species do not have the adequate binding energy to produce the necessary ‘hydride form’. The Ru electronic state is modified by the Cl that surrounds it, decreasing its ability to adsorb hydrogen. © 2018 Society of Chemical Industr