Influence of the anodizing process variables on the acidic properties of anodic alumina films

In the present work, the effect of the different variables involved in the process of aluminum anodizing on the total surface acidity of the samples obtained was studied. Aluminum foils were treated by the electro-chemical process of anodic anodizing within the following variable ranges: concentration=1.5-2.5 M; temperature=303-323 K; voltage=10-20 V; time=30-90 min. The total acidity of the samples was characterized by two different methods: acid-base titration using Hammet indicators and potentiometric titration. The results showed that anodizing time, temperature and concentration were the main variables that determined the surface acid properties of the samples, and to a lesser extent voltage. Acidity increased with increasing concentration of the electrolytic bath, whereas the rest of the variables had the opposite effect. Theresults obtained provide a novel tool for variable selection in order to use synthetized materials as catalytic supports, adding to previous research based on the morphology of alumina layers.Fil: Boldrini, Diego Emmanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Yañez, Maria Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentin

Synthesis of fatty acid methyl esters from pomace oil catalyzed by zinc stearate: A kinetic study of the transesterification and esterification reactions

In this work, the simultaneous transesterification and esterification reactions of olive pomace oil with methanol catalyzed by zinc stearate were studied. This catalyst is a crystalline solid at room temperature, but it is soluble in the reaction medium at reaction temperature. Zinc stearate has surfactant properties that cause the formation of an emulsion in the reaction system. The stability of the emulsion formed in the oil-methanol-catalyst system was compared to that in the FAME (fatty acid methyl esters)-methanol-catalyst system. It was observed that the emulsion formed in the presence of high amounts of FAME is much more unstable, which makes the catalyst easy to separate from the reaction products. The kinetics of esterification and transesterification were also studied. All the kinetic and equilibrium constants were determined with a complete model, considering the three stepwise reactions corresponding to the transesterification of triglycerides and the esterification of free fatty acids. The parameters obtained were used to model the operating conditions that would allow obtaining biodiesel that meets the quality standards.Fil: Alvarez Serafini, Mariana Soledad. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentin

Optimization of the enzymatic synthesis of pentyl oleate with lipase immobilized onto novel structured support

The term biorefinery is related to the sustainable production of value-added bioproducts and bioenergy from biomass. Esters from fatty acids are important compounds synthesized from by-products of the oleochemical industry. In agreement with the biorefinery concept, it is important to search for catalysts that reduce the consumption of energy and water, using moderate operation conditions and low reaction times. In this work, response surface methodology (RSM) was used to optimize the enzymatic synthesis of pentyl oleate using Candida antarctica lipase B (CALB) immobilized on a polyethylene-aluminum structured support. A factorial design was employed to evaluate the effects of several parameters on the ester yield. To obtain a model with a good fit, an approach to reaction mechanism and enzyme kinetics was taken into consideration. Experimental findings were correlated and explained using equations of a ping-pong bi-bi kinetic model and considering the inhibitory effects of both substrates. The developed model was consistent with the experimental data predicting an increase in pentyl oleate production with increasing temperature and a decrease with higher oleic acid amounts and alcohol to acid molar ratios. This model could be useful in a future industrial application of CALB/LLDPE/Al to minimize the costs in oleochemical biorefineries.Fil: Cavallaro, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Química; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Química; Argentin

Valorization of glycerol through the enzymatic synthesis of acylglycerides with high nutritional value

The production of specific acylglycerides from the selective esterification of glycerol is an attractive alternative for the valorization of this by-product of the biodiesel industry. In this way, products with high added value are generated, increasing the profitability of the overall process and reducing an associated environmental threat. In this work, nutritional and medically interesting glycerides were obtained by enzymatic esterification through a two-stage process. In the first stage, 1,3-dicaprin was obtained by the regioselective esterification of glycerol and capric acid mediated by the commercial biocatalyst Lipozyme RM IM. Under optimal reaction conditions, 73% conversion of fatty acids and 76% selectivity to 1,3-dicaprin was achieved. A new model to explain the participation of lipase in the acyl migration reaction is presented. It evaluates the conditions in the microenvironment of the active site of the enzyme during the formation of the tetrahedral intermediate. In the second stage, the esterification of the sn-2 position of 1,3-dicaprin with palmitic acid was performed using the lipase from Burkholderia cepacia immobilized on chitosan as the biocatalyst. A biocatalyst containing 3 wt % of lipase showed good activity to esterify the sn-2 position of 1,3-dicaprin. A mixture of acylglycerides consisting mainly of capric acid esterified at sn-1 and sn-3, and of palmitic acid at the sn-2 position was obtained as the reaction product. The influence of the biocatalyst mass, the reaction temperature, and the molar ratio of substrates were evaluated for this reaction using a factorial design. Simple models were used to adjust the consumption of reagents and the generation of different products. The reaction product contained between 76% and 90% of acylglycerides with high nutritional value, depending on the reaction conditions.Fil: Sanchez, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Química; Argentin

Synthesis of acylglycerides with high nutritional value by an enzymatic two step process

Acylglycerides are esters formed from glycerol and fatty acids. The structure of these glycerides affects their digestion and absorption. In this work, the synthesis of acylglycerides with high nutritional value by an enzymatic process in two stages is presented. In the first stage, the esterification ofglycerol and capric acid catalyzed by Lipozyme RM IM was carried out. In this reaction, 73% conversion of capric acid and 71% selectivity to 1,3-dicaprinwas achieved. The diglyceride was separated and purified efficiently by a simple liquid-liquid extraction procedure. The dicaprin was esterified with palmiticacid using Burkholderia cepacia lipase immobilized on chitosan as the catalyst. In this second stage, conversions of 1,3-dicaprin with values between 48 and87% and with high selectivity towards the esterification of the sn-2 position were achieved. The reaction product had between 76 and 90% of acylglycerides with high nutritional value, depending on the reaction conditions.Fil: Sanchez, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Ferreira, María Luján. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina. Universidad Nacional del Sur. Departamento de Ingeniería Química; Argentin

Study of Cu-Zn and Au/TiO2 Catalysts on Anodized Aluminum Monoliths for Hydrogen Generation and Purification

This work reports the preparation of Cu-Zn and Au/TiO2 catalysts on anodized aluminum monoliths(AAM). The structured catalysts were studied for the generation of H2 by methanol steam reforming (MSR) and its purification by preferential oxidation of CO (CO-PrOx). Initially, it was possible to generate a surface with whiskers and larger surface area by hydrothermal treatment of the AAM. Subsequently, the structured catalysts were synthesized by incipient wetness impregnation (IWI) and ydrothermal synthesis (HS). IWI synthesis allowed for the deposition of a larger amount of catalytic material than HS, with very good adhesion. The TiO2-IWI structured catalyst presented a homogeneous catalytic coating, with the presence of agglomerated particles. On theother hand, Cu-Zn-IWI showed good dispersion of the deposited particles with a homogeneous surface coating. EDX analysis corroborated the presence of Ti, Cu and Zn in all the catalytic surfaces. The incorporation of Au over TiO2-IWI structured catalysts was successfully performed by IWI using a colloidal solution of gold nanoparticles.MSR was studied over the developed metallic monoliths functionalized with Cu-Zn by the IWI method. The samples showed promising results in terms of activity, selectivity, and stability. Both diluted and concentrated methanol + water feeds were assayed. Complete methanol conversion was achieved for the diluted feed. Maximum methanol conversions of 55% with 60% H2 yield were measured when the concentrated feed was selected. Promising results were also achieved for the Au-based structured catalysts in the CO-PrOx in an H2- rich atmosphere. Although CO conversions of approximately 60% were achieved, operating with higher catalyst loadings would be recommended to reach the high CO conversions required for PrOx catalysts.Fil: Adrover, María Esperanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Boldrini, Diego Emmanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Jiménez Divins, Nuria. Universidad Politecnica de Catalunya; EspañaFil: Casanovas Hoste, Adria. Universidad Politecnica de Catalunya; EspañaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Lopez, Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Llorca Piqué, Jordi. Universidad Politecnica de Catalunya; Españ

Application of a Multienzymatic System from Natural Latex in Key Reactions for oil-Based Biorefineries

Oil-based biorefineries play a crucial role in the production of key platform chemicals that can be generated via biotechnological processes instead of a petrochemical route. This work focuses on the latex of the fruit of Araujia sericifera, which can be considered a multienzymatic system with applications in key reactions in oil-based biorefineries. The latex of Araujia sericifera (ASL) was used as a novel biocatalyst in the esterification of oleic acid and in the hydrolysis of triglycerides and p-nitrophenyl carboxylates. When ASL was compared to a commercial biocatalyst, it showed an excellent activity in the hydrolysis of soybean oil and p-nitropheyl laurate, and a comparable activity in the esterification reaction.Centro de Investigación de Proteínas Vegetales (CIProVe)Facultad de Ciencias Exacta

Application of a Multienzymatic System from Natural Latex in Key Reactions for oil-Based Biorefineries

Oil-based biorefineries play a crucial role in the production of key platform chemicals that can be generated via biotechnological processes instead of a petrochemical route. This work focuses on the latex of the fruit of Araujia sericifera, which can be considered a multienzymatic system with applications in key reactions in oil-based biorefineries. The latex of Araujia sericifera (ASL) was used as a novel biocatalyst in the esterification of oleic acid and in the hydrolysis of triglycerides and p-nitrophenyl carboxylates. When ASL was compared to a commercial biocatalyst, it showed an excellent activity in the hydrolysis of soybean oil and p-nitropheyl laurate, and a comparable activity in the esterification reaction.Centro de Investigación de Proteínas Vegetales (CIProVe)Facultad de Ciencias Exacta

Oxidación catalítica heterogénea de azul de metileno

En el presente trabajo se estudió ladegradación de azul de metileno (AM) utilizando como oxidante peróxido dehidrogeno, catalizado por oxido de niobio V. Se investigó el efecto del pH,transferencia de masa, tratamiento previo y reúso del catalizador, concentraciónde contaminante y lixiviación de Nb. Se buscaron las concentraciones optimas dereactivo y catalizador, siendo estas de 1.5% y 0.05% m/m, respectivamente.El catalizador y reactivo aplicadosen condiciones óptimas produjeron un alto porcentaje de degradación del AM entodos los ensayos realizados, mostrando la alta reactividad del procesopropuesto. Se observó que los procesos de tratamiento previo y reúso delcatalizador aumentan la reactividad del catalizador siendo un resultadoimportante para su aplicación.Fil: Toranzo, Pablo. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Prieto, Micaela. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Entelman, Valeria Daiana. Universidad Nacional del Sur. Departamento de Ingeniería Química; ArgentinaFil: Avila, Ana Julia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca; ArgentinaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaXXI Congreso Argentino de Catálisis y X Congreso de Catálisis del MercosurSanta FeArgentinaSociedad Argentina de CatálisisInstituto de Desarrollo Tecnológico para la Industria QuímicaInstituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera

Application of a Multienzymatic System from Natural Latex in Key Reactions for oil-Based Biorefineries

Oil-based biorefineries play a crucial role in the production of key platform chemicals that can be generated via biotechnological processes instead of a petrochemical route. This work focuses on the latex of the fruit of Araujia sericifera, which can be considered a multienzymatic system with applications in key reactions in oil-based biorefineries. The latex of Araujia sericifera (ASL) was used as a novel biocatalyst in the esterification of oleic acid and in the hydrolysis of triglycerides and p-nitrophenyl carboxylates. When ASL was compared to a commercial biocatalyst, it showed an excellent activity in the hydrolysis of soybean oil and p-nitropheyl laurate, and a comparable activity in the esterification reaction.Centro de Investigación de Proteínas Vegetales (CIProVe)Facultad de Ciencias Exacta