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Biodiesel process intensification by using static mixers tubular reactors / E. Santacesaria in Industrial & engineering chemistry research, Vol. 51 N° 26 (Juillet 2012) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 51 N° 26 (Juillet 2012) . - pp. 8777–8787 Titre : Biodiesel process intensification by using static mixers tubular reactors Type de document : texte imprimé Auteurs : E. Santacesaria, Auteur ; R. Turco, Auteur ; M. Tortorelli, Auteur Année de publication : 2012 Article en page(s) : pp. 8777–8787 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Biodiesel  process Résumé : Biodiesel is usually produced by reacting triglycerides, contained in vegetable oils, with methanol in the presence of KOH, NaOH, or related alkoxides as catalysts. In industry, the reaction is performed in stirred tank reactors and requires 1–2 h of reaction time being the reaction rate strongly affected by mass transfer limitation. We have recently shown, by using a Corrugated Plates Heat Exchanger Reactor, that a very high productivity (about 2 tons/day L) can be obtained by working at 60–100 °C thanks to the presence of an intense local “micromixing”. Moreover, we have recently tested the performances obtained in a tubular reactor filled with stainless steel spheres of different diameters. By opportunely changing the spheres diameters it is possible to obtain microchannels in a range of 300–1000 μm with an intense local micromixing. Again, thanks to micromixing we obtained very high productivities. However, in these last reactors the void portion of the reactor is low and the productivity per overall reactor volume is relatively low. It is possible to obtain better results, in terms of productivity, by filling the tubular reactor with stainless steel wool, being in this case the void fraction about 0.9. In the present work, some of the mentioned systems will be compared for their performances by using different amounts of KOH as catalyst (1 or 2% b.w. of oil). A dramatic change in biodiesel yield has been observed in all cases passing from 1 to 2% of catalyst independently of the reactants flow rate. These behaviors cannot be interpreted with the pseudomonophasic kinetic models, normally reported in the literature. At this purpose, for interpreting all the observed kinetic behaviors a new biphasic kinetic model, based on a reliable catalytic mechanism, has been developed. This model has been applied, first of all, to data reported in the literature related to runs performed in batch conditions with the scope of estimating the kinetic parameters, and then it has been applied to all the runs performed in continuous reactors with a satisfactory agreement. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie201640w [article] Biodiesel process intensification by using static mixers tubular reactors [texte imprimé] / E. Santacesaria, Auteur ; R. Turco, Auteur ; M. Tortorelli, Auteur . - 2012 . - pp. 8777–8787. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 26 (Juillet 2012) . - pp. 8777–8787 Mots-clés : Biodiesel  process Résumé : Biodiesel is usually produced by reacting triglycerides, contained in vegetable oils, with methanol in the presence of KOH, NaOH, or related alkoxides as catalysts. In industry, the reaction is performed in stirred tank reactors and requires 1–2 h of reaction time being the reaction rate strongly affected by mass transfer limitation. We have recently shown, by using a Corrugated Plates Heat Exchanger Reactor, that a very high productivity (about 2 tons/day L) can be obtained by working at 60–100 °C thanks to the presence of an intense local “micromixing”. Moreover, we have recently tested the performances obtained in a tubular reactor filled with stainless steel spheres of different diameters. By opportunely changing the spheres diameters it is possible to obtain microchannels in a range of 300–1000 μm with an intense local micromixing. Again, thanks to micromixing we obtained very high productivities. However, in these last reactors the void portion of the reactor is low and the productivity per overall reactor volume is relatively low. It is possible to obtain better results, in terms of productivity, by filling the tubular reactor with stainless steel wool, being in this case the void fraction about 0.9. In the present work, some of the mentioned systems will be compared for their performances by using different amounts of KOH as catalyst (1 or 2% b.w. of oil). A dramatic change in biodiesel yield has been observed in all cases passing from 1 to 2% of catalyst independently of the reactants flow rate. These behaviors cannot be interpreted with the pseudomonophasic kinetic models, normally reported in the literature. At this purpose, for interpreting all the observed kinetic behaviors a new biphasic kinetic model, based on a reliable catalytic mechanism, has been developed. This model has been applied, first of all, to data reported in the literature related to runs performed in batch conditions with the scope of estimating the kinetic parameters, and then it has been applied to all the runs performed in continuous reactors with a satisfactory agreement. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie201640w

Biphasic model describing soybean oil epoxidation with H2O2 in continuous reactors / E. Santacesaria in Industrial & engineering chemistry research, Vol. 51 N° 26 (Juillet 2012) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 51 N° 26 (Juillet 2012) . - pp. 8760–8767 Titre : Biphasic model describing soybean oil epoxidation with H2O2 in continuous reactors Type de document : texte imprimé Auteurs : E. Santacesaria, Auteur ; A. Renken, Auteur ; V. Russo, Auteur Année de publication : 2012 Article en page(s) : pp. 8760–8767 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Biphasic  Continuous  reactors Résumé : Epoxidized soybean oil (ESBO) is produced in industry by reacting soybean oil, at 60–70 °C, with hydrogen peroxide in the presence of formic or acetic acid. A small amount of sulphuric or phosphoric acid is necessary to catalyze the oxidation of the carboxylic acid to the corresponding per-carboxylic acid. Per-carboxylic acid, formed in situ, migrates from the aqueous phase to the oil phase where it spontaneously reacts with the double bonds to give an oxirane ring. This reaction is extremely exothermic (ΔH = −55 kcal/mol) and must be kept under thermal control. Two undesired side reactions can occur: the oxirane ring-opening and the hydrogen peroxide decomposition. In a previous work, a biphasic kinetic model for describing the epoxidation of soybean oil in fed or pulse-fed-batch reactors has been developed and the parameters of the model have been determined by mathematical regression analysis. In the present paper, the model has been adapted to simulate also kinetic runs performed in two continuous tubular reactors of different sizes, filled with spheres of stainless steel (AISI 316) used as static mixer. The agreement found, in simulating the continuous runs, validates the developed biphasic kinetic model. This model constitutes a valid base for the design of a continuous process and for promoting the process intensification. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie2016174 [article] Biphasic model describing soybean oil epoxidation with H2O2 in continuous reactors [texte imprimé] / E. Santacesaria, Auteur ; A. Renken, Auteur ; V. Russo, Auteur . - 2012 . - pp. 8760–8767. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 51 N° 26 (Juillet 2012) . - pp. 8760–8767 Mots-clés : Biphasic  Continuous  reactors Résumé : Epoxidized soybean oil (ESBO) is produced in industry by reacting soybean oil, at 60–70 °C, with hydrogen peroxide in the presence of formic or acetic acid. A small amount of sulphuric or phosphoric acid is necessary to catalyze the oxidation of the carboxylic acid to the corresponding per-carboxylic acid. Per-carboxylic acid, formed in situ, migrates from the aqueous phase to the oil phase where it spontaneously reacts with the double bonds to give an oxirane ring. This reaction is extremely exothermic (ΔH = −55 kcal/mol) and must be kept under thermal control. Two undesired side reactions can occur: the oxirane ring-opening and the hydrogen peroxide decomposition. In a previous work, a biphasic kinetic model for describing the epoxidation of soybean oil in fed or pulse-fed-batch reactors has been developed and the parameters of the model have been determined by mathematical regression analysis. In the present paper, the model has been adapted to simulate also kinetic runs performed in two continuous tubular reactors of different sizes, filled with spheres of stainless steel (AISI 316) used as static mixer. The agreement found, in simulating the continuous runs, validates the developed biphasic kinetic model. This model constitutes a valid base for the design of a continuous process and for promoting the process intensification. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie2016174

New process for producing epichlorohydrin via glycerol chlorination / E. Santacesaria in Industrial & engineering chemistry research, Vol. 49 N° 3 (Fevrier 2010) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 49 N° 3 (Fevrier 2010) . - pp. 964–970 Titre : New process for producing epichlorohydrin via glycerol chlorination Type de document : texte imprimé Auteurs : E. Santacesaria, Auteur ; R. Tesser, Auteur ; M. Di Serio, Auteur Année de publication : 2010 Article en page(s) : pp. 964–970 Note générale : Industrial Chemistry Langues : Anglais (eng) Mots-clés : Glycerol--Epichlorohydrin--Chlorination Résumé : The strong growth of biodiesel production occurring in the last years has determined the availability of a great amount of the byproduct glycerol. Many researches in the world are therefore oriented to find new possible uses for glycerol also with the aim of reducing the cost of biodiesel. In this paper the chlorination of glycerol with gaseous hydrochloric acid to obtain 1,3-dichlorohydrin and then epichlorohydrin will be described. All the advantages of this process will be examined and discussed. The behavior of the different proposed catalysts (normally compounds containing carboxylic acid groups), the reaction kinetics, the effect of the catalyst concentration, the effect of HCl pressure, the vapor−liquid phase equilibria of the reaction products in the reaction environment, and the most convenient operative conditions have been studied, concluding with useful suggestions for the design of the industrial plants. Note de contenu : Bibiogr. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie900650x [article] New process for producing epichlorohydrin via glycerol chlorination [texte imprimé] / E. Santacesaria, Auteur ; R. Tesser, Auteur ; M. Di Serio, Auteur . - 2010 . - pp. 964–970. Industrial Chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 3 (Fevrier 2010) . - pp. 964–970 Mots-clés : Glycerol--Epichlorohydrin--Chlorination Résumé : The strong growth of biodiesel production occurring in the last years has determined the availability of a great amount of the byproduct glycerol. Many researches in the world are therefore oriented to find new possible uses for glycerol also with the aim of reducing the cost of biodiesel. In this paper the chlorination of glycerol with gaseous hydrochloric acid to obtain 1,3-dichlorohydrin and then epichlorohydrin will be described. All the advantages of this process will be examined and discussed. The behavior of the different proposed catalysts (normally compounds containing carboxylic acid groups), the reaction kinetics, the effect of the catalyst concentration, the effect of HCl pressure, the vapor−liquid phase equilibria of the reaction products in the reaction environment, and the most convenient operative conditions have been studied, concluding with useful suggestions for the design of the industrial plants. Note de contenu : Bibiogr. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie900650x