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Oxidative desulfurization I / Paolo De Filippis in Industrial & engineering chemistry research, Vol. 49 N° 10 (Mai 2010) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 49 N° 10 (Mai 2010) . - pp. 4594–4600 Titre : Oxidative desulfurization I : peroxyformic acid oxidation of benzothiophene and dibenzothiophene Type de document : texte imprimé Auteurs : Paolo De Filippis, Auteur ; Marco Scarsella, Auteur ; Nicola Verdone, Auteur Année de publication : 2010 Article en page(s) : pp. 4594–4600 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Peroxyformic  acid  Oxidation Résumé : Oxidative desulfurization routes appear among the most promising methods for obtaining ultralow-sulfur diesel fuels requested worldwide by environmental legislation. In this work, the oxidation kinetic of benzo- and dibenzothiophene with the oxidizing system constituted by hydrogen peroxide and formic acid was studied in isothermal conditions at 40 °C. Since the oxidation occurs in a heterophasic system, both physical and chemical phenomena play an important rule. The aim of this work was to interpret the obtained experimental conversions with a model able to capture the influence of both mass transfer and chemical kinetics. The results allowed verification that the oxidation reaction occurs in the slow liquid−liquid reaction regime and chemical kinetics is the controlling step. The identified values of the intrinsic kinetic constants for the oxidation of benzo- and dibenzothiophene are 2.255 × 10−1 and 1.206 × 100 m3 kmol−1 s−1, respectively. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie9017622 [article] Oxidative desulfurization I : peroxyformic acid oxidation of benzothiophene and dibenzothiophene [texte imprimé] / Paolo De Filippis, Auteur ; Marco Scarsella, Auteur ; Nicola Verdone, Auteur . - 2010 . - pp. 4594–4600. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 10 (Mai 2010) . - pp. 4594–4600 Mots-clés : Peroxyformic  acid  Oxidation Résumé : Oxidative desulfurization routes appear among the most promising methods for obtaining ultralow-sulfur diesel fuels requested worldwide by environmental legislation. In this work, the oxidation kinetic of benzo- and dibenzothiophene with the oxidizing system constituted by hydrogen peroxide and formic acid was studied in isothermal conditions at 40 °C. Since the oxidation occurs in a heterophasic system, both physical and chemical phenomena play an important rule. The aim of this work was to interpret the obtained experimental conversions with a model able to capture the influence of both mass transfer and chemical kinetics. The results allowed verification that the oxidation reaction occurs in the slow liquid−liquid reaction regime and chemical kinetics is the controlling step. The identified values of the intrinsic kinetic constants for the oxidation of benzo- and dibenzothiophene are 2.255 × 10−1 and 1.206 × 100 m3 kmol−1 s−1, respectively. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie9017622

Peroxyformic acid formation / Paolo De Filippis in Industrial & engineering chemistry research, Vol. 48 N°3 (Février 2009) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 48 N°3 (Février 2009) . - p. 1372–1375 Titre : Peroxyformic acid formation : a kinetic study Type de document : texte imprimé Auteurs : Paolo De Filippis, Auteur ; Marco Scarsella, Auteur ; Nicola Verdone, Auteur Année de publication : 2009 Article en page(s) : p. 1372–1375 Note générale : Chemical engineering Langues : Anglais (eng) Mots-clés : Peroxyformic  acid  --  Kinetic  study  Chemical  industry Résumé : Peroxyformic acid has been recently assuming a growing importance due to the versatile oxidizing properties in several applications in the chemical industry. However, quite surprisingly, a lack of data exists about the kinetics of formation of this compound, an even more singular event considering that the acid, when used, is generally produced in situ via the reaction between formic acid and hydrogen peroxide. This paper is a contribution to fill this gap. A series of batch experiments were carried out to measure the conversion rate in the peroxyformic acid formation reaction in the temperature range 30−60 °C. The results from experiments were successfully interpreted through a kinetic mechanism consisting of the reversible formation of the peroxyformic acid and its irreversible decomposition to CO2 and H2O, both catalyzed by hydrogen ions. With the considered kinetic mechanism, a pre-exponential factor of 13065.1 L6 mol−2 s−1 and an activation energy of 43524.2 J mol−1 were calculated. This last value and enthalpy and entropy of reaction derived from the kinetic data are in quite good accordance with the limited literature data available on this subject. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie801163j [article] Peroxyformic acid formation : a kinetic study [texte imprimé] / Paolo De Filippis, Auteur ; Marco Scarsella, Auteur ; Nicola Verdone, Auteur . - 2009 . - p. 1372–1375. Chemical engineering Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 48 N°3 (Février 2009) . - p. 1372–1375 Mots-clés : Peroxyformic  acid  --  Kinetic  study  Chemical  industry Résumé : Peroxyformic acid has been recently assuming a growing importance due to the versatile oxidizing properties in several applications in the chemical industry. However, quite surprisingly, a lack of data exists about the kinetics of formation of this compound, an even more singular event considering that the acid, when used, is generally produced in situ via the reaction between formic acid and hydrogen peroxide. This paper is a contribution to fill this gap. A series of batch experiments were carried out to measure the conversion rate in the peroxyformic acid formation reaction in the temperature range 30−60 °C. The results from experiments were successfully interpreted through a kinetic mechanism consisting of the reversible formation of the peroxyformic acid and its irreversible decomposition to CO2 and H2O, both catalyzed by hydrogen ions. With the considered kinetic mechanism, a pre-exponential factor of 13065.1 L6 mol−2 s−1 and an activation energy of 43524.2 J mol−1 were calculated. This last value and enthalpy and entropy of reaction derived from the kinetic data are in quite good accordance with the limited literature data available on this subject. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie801163j