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Assessment of noncatalytic biodiesel synthesis using supercritical reaction conditions / Tanawan Pinnarat in Industrial & engineering chemistry research, Vol. 47 N°18 (Septembre 2008) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 47 N°18 (Septembre 2008) . - p. 6801–6808 Titre : Assessment of noncatalytic biodiesel synthesis using supercritical reaction conditions Type de document : texte imprimé Auteurs : Tanawan Pinnarat, Auteur ; Phillip E. Savage Année de publication : 2008 Article en page(s) : p. 6801–6808 Note générale : Chemical engineering Langues : Anglais (eng) Mots-clés : Biodiesel  fuel  Kinetics Résumé : This article reviews the relatively new field of supercritical fluid phase synthesis of biodiesel fuel. We assess the current state of the art and then suggest several directions for new or additional research that would lead to important advances in this field. Biodiesel synthesis at supercritical conditions is technologically feasible and perhaps economically competitive with conventional synthesis routes for low-cost feedstocks such as waste cooking oil. A better understanding of the reaction kinetics (both metal-catalyzed and uncatalyzed) and phase behavior (e.g., location of liquid−liquid−vapor and liquid−vapor regions and critical temperature and pressure as they change during the course of the reaction) is needed. Additionally, there is a need for more detailed analysis of the economics, energy requirements, and environmental impacts of the supercritical process relative to conventional technology. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie800542k [article] Assessment of noncatalytic biodiesel synthesis using supercritical reaction conditions [texte imprimé] / Tanawan Pinnarat, Auteur ; Phillip E. Savage . - 2008 . - p. 6801–6808. Chemical engineering Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 47 N°18 (Septembre 2008) . - p. 6801–6808 Mots-clés : Biodiesel  fuel  Kinetics Résumé : This article reviews the relatively new field of supercritical fluid phase synthesis of biodiesel fuel. We assess the current state of the art and then suggest several directions for new or additional research that would lead to important advances in this field. Biodiesel synthesis at supercritical conditions is technologically feasible and perhaps economically competitive with conventional synthesis routes for low-cost feedstocks such as waste cooking oil. A better understanding of the reaction kinetics (both metal-catalyzed and uncatalyzed) and phase behavior (e.g., location of liquid−liquid−vapor and liquid−vapor regions and critical temperature and pressure as they change during the course of the reaction) is needed. Additionally, there is a need for more detailed analysis of the economics, energy requirements, and environmental impacts of the supercritical process relative to conventional technology. En ligne : http://pubs.acs.org/doi/abs/10.1021/ie800542k

Effect of metals on supercritical water gasification of cellulose and lignin / Fernando L. P. Resende in Industrial & engineering chemistry research, Vol. 49 N° 6 (Mars 2010) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 49 N° 6 (Mars 2010) . - pp. 2694–2700 Titre : Effect of metals on supercritical water gasification of cellulose and lignin Type de document : texte imprimé Auteurs : Fernando L. P. Resende, Auteur ; Phillip E. Savage, Auteur Année de publication : 2010 Article en page(s) : pp. 2694–2700 Note générale : Idustrial Chemistry Langues : Anglais (eng) Mots-clés : Metals  Supercritical  Water  Gasification  Cellulose  Lignin Résumé : We gasified cellulose and lignin in supercritical water, using quartz reactors, and quantified the catalytic effect of metals by adding them to these reactors in different forms. We used nickel, iron, copper, zinc, and zirconium wires, ruthenium powder, and Raney nickel slurry. The presence of metals was more likely to increase gas yields to a measurable extent when the catalyst surface area/biomass weight ratio was at least 15 mm2/mg (5.0 wt % biomass loading in our experiments). Nickel and copper typically provided higher gas yields at 5.0 wt % loading, and nickel provided the highest H2 yields at 1.0 wt % loading. SCWG at 500 °C with nickel at 240 mm2/mg generated 16 mmol/g of H2 from cellulose. CH4 yields were not strongly influenced by the presence of metals. With nickel wires in the reactor, gas with about 40−50% of the energy content in the original biomass was produced from cellulose and lignin. All of the metals tested except copper produced H2 from water when exposed to SCWG conditions with no biomass. It is important that this background H2 formation be accounted for when interpreting results from SCWG experiments in the presence of metals. Exposure of nickel wires to supercritical water did not reduce their activity for H2 production. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie901928f [article] Effect of metals on supercritical water gasification of cellulose and lignin [texte imprimé] / Fernando L. P. Resende, Auteur ; Phillip E. Savage, Auteur . - 2010 . - pp. 2694–2700. Idustrial Chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 6 (Mars 2010) . - pp. 2694–2700 Mots-clés : Metals  Supercritical  Water  Gasification  Cellulose  Lignin Résumé : We gasified cellulose and lignin in supercritical water, using quartz reactors, and quantified the catalytic effect of metals by adding them to these reactors in different forms. We used nickel, iron, copper, zinc, and zirconium wires, ruthenium powder, and Raney nickel slurry. The presence of metals was more likely to increase gas yields to a measurable extent when the catalyst surface area/biomass weight ratio was at least 15 mm2/mg (5.0 wt % biomass loading in our experiments). Nickel and copper typically provided higher gas yields at 5.0 wt % loading, and nickel provided the highest H2 yields at 1.0 wt % loading. SCWG at 500 °C with nickel at 240 mm2/mg generated 16 mmol/g of H2 from cellulose. CH4 yields were not strongly influenced by the presence of metals. With nickel wires in the reactor, gas with about 40−50% of the energy content in the original biomass was produced from cellulose and lignin. All of the metals tested except copper produced H2 from water when exposed to SCWG conditions with no biomass. It is important that this background H2 formation be accounted for when interpreting results from SCWG experiments in the presence of metals. Exposure of nickel wires to supercritical water did not reduce their activity for H2 production. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie901928f

Hydration of 1-phenyl-1-propyne in high-temperature water with catalysis by water-tolerant lewis acids / Rebacz, Natalie A. in Industrial & engineering chemistry research, Vol. 49 N° 2 (Janvier 2010) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 49 N° 2 (Janvier 2010) . - pp 535-540 Titre : Hydration of 1-phenyl-1-propyne in high-temperature water with catalysis by water-tolerant lewis acids Type de document : texte imprimé Auteurs : Rebacz, Natalie A., Auteur ; Phillip E. Savage, Auteur Année de publication : 2010 Article en page(s) : pp 535-540 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Hydration  phenyl  propyne  Water  tolerant  Lewis  acids. Résumé : We explore various aspects of alkyne hydration in high temperature water catalyzed by water-tolerant Lewis acids through experimentation with the hydration of 1-phenyl-1-propyne. Experiments comparing indium triflate, scandium triflate, ytterbium triflate, sulfuric acid, and hydrochloric acid indicate that indium triflate is the most active catalyst toward this reactive system of those tested. Experiments with quartz and stainless steel reactors in conjunction with quartz and stainless steel additive demonstrate that reactor material of construction has no appreciable effect upon the reaction. The reaction is first order in both catalyst and alkyne. We further determine the kinetic parameter k for four temperatures (150, 175, 200, and 225 °C), and find that the frequency factor is 108.8±0.3 L/(mol s) and the activation energy is 21.4 ± 0.6 kcal/mol for this transformation. This is the first example of alkyne hydration in high-temperature water catalyzed by water-tolerant Lewis acids. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie9017513 [article] Hydration of 1-phenyl-1-propyne in high-temperature water with catalysis by water-tolerant lewis acids [texte imprimé] / Rebacz, Natalie A., Auteur ; Phillip E. Savage, Auteur . - 2010 . - pp 535-540. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 49 N° 2 (Janvier 2010) . - pp 535-540 Mots-clés : Hydration  phenyl  propyne  Water  tolerant  Lewis  acids. Résumé : We explore various aspects of alkyne hydration in high temperature water catalyzed by water-tolerant Lewis acids through experimentation with the hydration of 1-phenyl-1-propyne. Experiments comparing indium triflate, scandium triflate, ytterbium triflate, sulfuric acid, and hydrochloric acid indicate that indium triflate is the most active catalyst toward this reactive system of those tested. Experiments with quartz and stainless steel reactors in conjunction with quartz and stainless steel additive demonstrate that reactor material of construction has no appreciable effect upon the reaction. The reaction is first order in both catalyst and alkyne. We further determine the kinetic parameter k for four temperatures (150, 175, 200, and 225 °C), and find that the frequency factor is 108.8±0.3 L/(mol s) and the activation energy is 21.4 ± 0.6 kcal/mol for this transformation. This is the first example of alkyne hydration in high-temperature water catalyzed by water-tolerant Lewis acids. DEWEY : 660 ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie9017513

Hydrothermal Decarboxylation of Pentafluorobenzoic Acid and Quinolinic Acid / Jie Fu in Industrial & engineering chemistry research, Vol. 48 N° 23 (Décembre 2009) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 48 N° 23 (Décembre 2009) . - pp. 10467–10471 Titre : Hydrothermal Decarboxylation of Pentafluorobenzoic Acid and Quinolinic Acid Type de document : texte imprimé Auteurs : Jie Fu, Auteur ; Phillip E. Savage, Auteur ; Xiuyang Lu, Auteur Année de publication : 2010 Article en page(s) : pp. 10467–10471 Note générale : Industrial chemistry Langues : Anglais (eng) Mots-clés : Hydrothermal--Decarboxylation--Pentafluorobenzoic--Acid--Quinolinic--Acid Résumé : We report herein the first kinetics studies of hydrothermal decarboxylation of a fully halogenated benzoic acid and a heterocyclic aromatic diacid. Decarboxylation was the only reaction path observed, and there was no evidence of dehalogenation. Experiments at different initial reactant concentrations and different batch holding times revealed that both compounds exhibited first-order kinetics. Experiments at different temperatures showed that the first-order rate constants displayed Arrhenius behavior with activation energies of 157 kJ mol−1 for pentafluorobenzoic acid decarboxylation and 141 kJ mol−1 for quinolinic acid decarboxylation. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie901182y [article] Hydrothermal Decarboxylation of Pentafluorobenzoic Acid and Quinolinic Acid [texte imprimé] / Jie Fu, Auteur ; Phillip E. Savage, Auteur ; Xiuyang Lu, Auteur . - 2010 . - pp. 10467–10471. Industrial chemistry Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 48 N° 23 (Décembre 2009) . - pp. 10467–10471 Mots-clés : Hydrothermal--Decarboxylation--Pentafluorobenzoic--Acid--Quinolinic--Acid Résumé : We report herein the first kinetics studies of hydrothermal decarboxylation of a fully halogenated benzoic acid and a heterocyclic aromatic diacid. Decarboxylation was the only reaction path observed, and there was no evidence of dehalogenation. Experiments at different initial reactant concentrations and different batch holding times revealed that both compounds exhibited first-order kinetics. Experiments at different temperatures showed that the first-order rate constants displayed Arrhenius behavior with activation energies of 157 kJ mol−1 for pentafluorobenzoic acid decarboxylation and 141 kJ mol−1 for quinolinic acid decarboxylation. ISSN : 0888-5885 En ligne : http://pubs.acs.org/doi/abs/10.1021/ie901182y

Mechanistic modeling of hydrolysis and esterification for biofuel processes / Shujauddin Changi in Industrial & engineering chemistry research, Vol. 50 N° 22 (Novembre 2011) 

Public ISBD [article]  in Industrial & engineering chemistry research > Vol. 50 N° 22 (Novembre 2011) . - pp. 12471-12478 Titre : Mechanistic modeling of hydrolysis and esterification for biofuel processes Type de document : texte imprimé Auteurs : Shujauddin Changi, Auteur ; Tanawan Pinnarat, Auteur ; Phillip E. Savage, Auteur Année de publication : 2012 Article en page(s) : pp. 12471-12478 Note générale : Chimie industrielle Langues : Anglais (eng) Mots-clés : Esterification  Hydrolysis  Modeling Résumé : We have elucidated the mechanism for ethyl oleate hydrolysis in high temperature water and its reverse reaction, oleic acid esterification in near- and supercritical ethanol in the absence of any other added compounds. Both reactions are acid catalyzed. H+ (from dissociation of water and oleic acid) and oleic acid serve as catalysts for hydrolysis and H+ alone is the catalyst for esterification. The rate equation arising from the proposed mechanism provided a good fit of experimental conversion data for both hydrolysis and esterification. The rate equation accurately predicted the influence of pH on hydrolysis for acidic and near-neutral conditions. The mechanistic model exhibits the ability to make quantitatively accurate predictions within and outside the original parameter space, especially for a multicomponent system. Sensitivity analysis shows that the values of the dissociation constant of oleic acid in ethanol, water, and ethanol-water systems strongly influence the predicted conversions. There is a need for experimental measurement of pKa for fatty acids in both water and alcohols at elevated temperatures. DEWEY : 660 ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=24745720 [article] Mechanistic modeling of hydrolysis and esterification for biofuel processes [texte imprimé] / Shujauddin Changi, Auteur ; Tanawan Pinnarat, Auteur ; Phillip E. Savage, Auteur . - 2012 . - pp. 12471-12478. Chimie industrielle Langues : Anglais (eng) in Industrial & engineering chemistry research > Vol. 50 N° 22 (Novembre 2011) . - pp. 12471-12478 Mots-clés : Esterification  Hydrolysis  Modeling Résumé : We have elucidated the mechanism for ethyl oleate hydrolysis in high temperature water and its reverse reaction, oleic acid esterification in near- and supercritical ethanol in the absence of any other added compounds. Both reactions are acid catalyzed. H+ (from dissociation of water and oleic acid) and oleic acid serve as catalysts for hydrolysis and H+ alone is the catalyst for esterification. The rate equation arising from the proposed mechanism provided a good fit of experimental conversion data for both hydrolysis and esterification. The rate equation accurately predicted the influence of pH on hydrolysis for acidic and near-neutral conditions. The mechanistic model exhibits the ability to make quantitatively accurate predictions within and outside the original parameter space, especially for a multicomponent system. Sensitivity analysis shows that the values of the dissociation constant of oleic acid in ethanol, water, and ethanol-water systems strongly influence the predicted conversions. There is a need for experimental measurement of pKa for fatty acids in both water and alcohols at elevated temperatures. DEWEY : 660 ISSN : 0888-5885 En ligne : http://cat.inist.fr/?aModele=afficheN&cpsidt=24745720

A rapid hot-injection method for the improved hydrothermal synthesis of CdSe nanoparticles / Juandria V. Williams in Industrial & engineering chemistry research, Vol. 48 N° 9 (Mai 2009) 

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