Papers by Martin Nicolas Gatti
Processes
The wide availability of crude glycerol and its low market price make this by-product of the biod... more The wide availability of crude glycerol and its low market price make this by-product of the biodiesel industry a promising raw material for obtaining high-value-added products through catalytic conversion processes. This work studied the effect of the composition of different industrial crude glycerol samples on the catalytic hydrogenolysis to 1,2-propylene glycol. A nickel catalyst supported on a silica–carbon composite was employed with this purpose. This catalyst proved to be active, selective to 1,2-propylene glycol and stable in the glycerol hydrogenolysis reaction in the liquid phase when analytical glycerol (99% purity) was employed. In order to determine the effect of crude glycerol composition on the activity, selectivity and stability of this catalyst, industrial crude glycerol samples were characterized by identifying and quantifying the impurities present in them (methanol, NaOH, NaCl and NaCOOH). Reaction tests were carried out with aqueous solutions of analytical glyc...
Materials
Research on the use of biomass resources for the generation of energy and chemical compounds is o... more Research on the use of biomass resources for the generation of energy and chemical compounds is of great interest worldwide. The development and growth of the biodiesel industry has led to a parallel market for the supply of glycerol, its main by-product. Its wide availability and relatively low cost as a raw material make glycerol a basic component for obtaining various chemical products and allows for the development of a biorefinery around biodiesel plants, through the technological integration of different production processes. This work proposes a review of one of the reactions of interest in the biorefinery environment: the hydrogenolysis of glycerol to 1,2-propylene glycol. The article reviews more than 300 references, covering literature from about 20 years, focusing on the heterogeneous catalysts used for the production of glycol. In this sense, from about 175 catalysts, between bulk and supported ones, were revised and discussed critically, based on noble metals, such as R...
Estos resultados forman parte de uno de los objetivos de mi beca posdoctoral que consiste en la o... more Estos resultados forman parte de uno de los objetivos de mi beca posdoctoral que consiste en la obtención de productos de alto valor agregado a partir de glicerol mediante reacciones de hidrogenólisis en fase líquida. En particular, a la producción de 1-propanol (1-POH) a partir de la hidrogenólisis de glicerol crudo en fase líquida empleando catalizadores de Ni. Para ello, se desarrollaron dos catalizadores de Ni con diferentes soportes; una alúmina (γ-Al2O3) y un composito de carbón impregnado con fósforo (CS-P). Los mismos fueron caracterizados para determinar sus propiedades ácidas y fases metálicas. Con el catalizador Ni/γ-Al2O3, que presentó pequeñas partículas de Ni interactuando con los sitios ácidos del soporte, fue posible obtener una conversión completa del glicerol crudo con alta selectividad a 1,2-propilenglicol (1,2-PG) (87%) a 220 °C, que resulta ser el compuesto intermediario para la obtención del 1-POH. Con el catalizador Ni/CS-P, la presencia de especies AlPOx y la...
Reactions
Humanity’s growing dependence on non-renewable resources and the ensuing environmental impact thu... more Humanity’s growing dependence on non-renewable resources and the ensuing environmental impact thus generated have spurred the search for alternatives to replace chemicals and energy obtained from petroleum derivatives. Within the group of biofuels, biodiesel has managed to expand worldwide at considerable levels, going from 20 million tn/year in 2010 to 47 million tn/year in 2022, boosting the supply of glycerol, a by-product of its synthesis that can be easily used as a renewable, clean, low-cost raw material for the manufacture of products for the chemical industry. The hydrogenolysis of glycerol leads to the production of glycols, 1,2-propylene glycol (1,2-PG) and 1,3-propylene glycol (1,3-PG). In particular, 1,3-PG has the highest added value and has multiple uses including its application as an additive in the polymer industry, the manufacture of cosmetics, cleaning products, cooling liquids, etc. This review focuses on the study of the hydrogenolysis of glycerol for the produc...
Se estudio la sintesis y caracterizacion de un material mesoporoso de base carbonosa (SiO 2 -C) e... more Se estudio la sintesis y caracterizacion de un material mesoporoso de base carbonosa (SiO 2 -C) el cual fue sometido a severas condiciones hidrotermicas y posteriomente se lo evaluo como soporte catalitico. El material (SiO 2 -C) fue obtenido a partir de la co-gelificacion de TEOS y una resina fenolica. Entre sus caracteristicas presenta una estrecha distribucion de tamano de poro en la region meso-porosa, un PZC = 7 y neutralidad superficial. Para evaluarlo cataliticamente se prepararon catalizadores de Ru y Ni soportados sobre el material SiO 2 -C que resultaron activos y selectivos en la reaccion de hidrogenolisis del glicerol en fase liquida a 200°C para producir glicoles (propilenglicol y etilenglicol). El catalizador de Ru/SiO 2 -C (Ru/SC) resulto el mas activo y estable por 24 hs de reaccion.
En este trabajo se estudio la modificacion de un soporte de silice-carbon con precursores de Al, ... more En este trabajo se estudio la modificacion de un soporte de silice-carbon con precursores de Al, P y P-Al para mejorar la selectividad de catalizadores de Ni hacia la formacion de 1-propanol, por hidrogenolisis de glicerol en fase acuosa. Los resultados mostraron que la modificacion con P y P-Al producen un incremento en la acidez superficial y la formacion de una fase Ni2P.
Preparación del soporte SC: El composito de sílice-carbón (SC) fue sintetizado acorde a las mater... more Preparación del soporte SC: El composito de sílice-carbón (SC) fue sintetizado acorde a las materias primas y procedimiento detallado en un trabajo previo [24]. Se empleó tetra-brought to you by CORE View metadata, citation and similar papers at core.ac.uk
Fil: Gatti, Martin Nicolas. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Ci... more Fil: Gatti, Martin Nicolas. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico la Plata. Centro de Investigacion y Desarrollo En Ciencias Aplicadas; Argentina
Resumen En el presente trabajo se estudió el proceso de funcionalización de un composito mesoporo... more Resumen En el presente trabajo se estudió el proceso de funcionalización de un composito mesoporoso de SiO 2-C utilizando ácido nítrico como agente oxidante y diferentes condiciones de temperatura (80-100°C), concentración de ácido (30-90% p/p) y tiempo de funcionalización (2-6 h). Aumentar la acidez superficial resulta de interés cuando los materiales se utilizan como soportes catalíticos. Aumentar los sitios activos por la presencia de grupos oxigenados favorece la interacción del precursor metálico y el soporte, y son claves en el diseño de catalizadores bifuncionales. Los resultados muestran que condiciones de 100°C, con una concentración 60% en peso de ácido y un tiempo de 2 h, provocan una pérdida significativa de la superficie específica debido a la gasificación del carbón y colapso de microporos. Se determinó que el tratamiento de funcionalización del composito sílice-carbón a 80°C durante 2 h utilizando una solución de HNO 3 al 60% en peso, resulta efectivo para proporcionar mayor acidez superficial sin pérdida de superficie específica y con grupos oxigenados superficiales que otorgan acidez tipo Lewis.
En trabajos previos, hemos preparado un catalizador de níquel soportado en un composito de sílice... more En trabajos previos, hemos preparado un catalizador de níquel soportado en un composito de sílice-carbón, demostrando que el mismo es activo, selectivo y estable en la reacción de hidrogenólisis de glicerol para la producción de bio-propilenglicol. Con el objetivo de mejorar la actividad de este catalizador, en este trabajo estudiamos la modificación en la formulación del catalizador mediante dos estrategias: por un lado, la modificación de su acidez a través de un proceso de funcionalización del carbón presente en el soporte, y por otro lado, la modificación de la fase metálica a partir de la adición de Zn con una técnica de preparación controlada, que permite, de manera selectiva la adición de pequeñas cantidades de otro metal. La funcionalización del soporte empleando ácido nítrico al 60% en peso como agente oxidante, permitió incrementar el número de sitios ácidos en el soporte del tipo Lewis, sin pérdida de superficie específica. La adición de Zn en el rango 1,1 a 1,8 % en peso genera la formación de un sitio activo compuesto por una aleación de -NiZn responsable de un incremento en la actividad catalítica. Cuando la adición de Zn alcanza al 2.8% en peso se genera una nueva fase metálica correspondiente a la fase tetragonal 1-NiZn que causa una caída en la actividad. Los resultados indican que la presencia de la aleación -NiZn tiene un efecto más significativo hacia el incremento de la actividad y de la selectividad a la ruptura de enlaces CO que el efecto de la acidez superficial del soporte sobre la actividad de deshidratación, siendo ambas rutas de reacción conducentes a la formación de bio-propilenglicol.
Catalysis Today, 2020
The aim of this work was to investigate the catalytic properties of nickel over a carbon-based su... more The aim of this work was to investigate the catalytic properties of nickel over a carbon-based support modified with phosphorus for the hydrogenolysis of glycerol to obtain 1-propanol. For this, a series of nickel phosphide catalysts with different compositions were prepared employing Al(H 2 PO 4) 3 and NiCl 2 supported on mesoporous carbon and characterized by N 2 adsorption-desorption, acid-base properties measurements, TEM, XRD and XAFS analysis. These Ni catalysts presented different phases (Ni x P y , NiPO x , AlPO x), responsible of the increase in surface acidity, which depended on the Al(H 2 PO 4) 3 content. For Al(H 2 PO 4) 3 contents between 4 and 10 wt.%, an increase in surface acidity occurs that favors both the conversion and the selectivity of glycerol towards 1-propanol. These results show that the presence of the phosphates is necessary to reach high levels of catalytic activity. However, for Al(H 2 PO 4) 3 contents higher than 10 wt.%, a fall or loss of selectivity was produced due to the strong contribution of dehydration reactions on the support acid sites. The Ni/CPAl(10) catalyst, allows reaching 97 % conversion of glycerol with a selectivity of 74 % towards 1-propanol, employing an 80 wt.% glycerol aqueous solution, after 6 h of reaction.
Catalysts, 2020
The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycero... more The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycerol hydrogenolysis in liquid phase and find an alternative to the use of noble metals by employing Ni catalysts. Two Ni catalysts with different supports, alumina (γ-Al2O3), and a phosphorous-impregnated carbon composite (CS-P) were studied and characterized in order to determine their acid properties and metallic phases. With the Ni/γ-Al2O3 catalyst, which presented small particles of metallic Ni interacting with the acid sites of the support, it was possible to obtain a complete conversion of crude glycerol with high selectivity towards 1,2-propylene glycol (1,2 PG) (87%) at 220 °C whereas with the Ni/CS-P catalyst, the presence of AlPOx species and the Ni2P metallic phase supplied acidity to the catalyst, which promoted the C-O bond cleavage reaction of the secondary carbon of 1,2 PG to obtain 1-POH with very high selectivity (71%) at 260 °C. It was found that the employment of two cons...
Esta tesis plantea la preparación y caracterización de catalizadores para la conversión de glicer... more Esta tesis plantea la preparación y caracterización de catalizadores para la conversión de glicerol a biopropilenglicol. En el capítulo 1 se presentan conceptos básicos de biomasa, su transformación y la posibilidad, a partir de ella, de sustituir algunos de los productos químicos derivados del petróleo que la sociedad utiliza actualmente. En este marco, es interesante plantear la utilización del glicerol como recurso proveniente de la biomasa obtenido a partir de la producción de biodiesel. El 1,2-propilenglicol (1,2-PG) es tradicionalmente obtenido por hidratación del óxido de propileno (OP), compuesto que se obtiene vía petroquímica. El proceso de transformación del glicerol para producir 1,2 PG generaría un reemplazo de procesos de síntesis petroquímicos por procesos que valorizan fuentes renovables. El precio del 1,2-PG en el mercado es mucho mayor que el precio del glicerol, lo cual estimula el desarrollo de un nuevo proceso químico que permita la producción de 1,2-PG a partir...
International Journal of Hydrogen Energy, 2017
This work studies 2 wt% Pt catalysts. The support is a SiO 2-C composite whose main features are ... more This work studies 2 wt% Pt catalysts. The support is a SiO 2-C composite whose main features are a high specific surface due to its mesoporosity, a higher thermal stability than the C support, and the absence of surface acid sites which could promote the dehydration reactions that produce coke precursors. The Pt/SiO 2-C catalyst has very small metallic particles (d va ¼ 1.37 nm) that favor the CeC bond cleavage reactions which allow obtaining total gas conversion at 450 C. With this catalyst, it is possible to obtain high yields to H 2 , between 4 and 5, which indicates that the active sites promote the WGS reaction, even with glycerol concentrations of 30 and 50%. Pt/SiO 2-C is a very stable catalyst since it loses only 10% of its initial activity after 66 h on stream and is resistant to sintering and coke deposition.
Catalysis Today, 2017
The development of catalytic materials, hydrothermally stable and selective to the desired produc... more The development of catalytic materials, hydrothermally stable and selective to the desired products, is still a challenge. The aim of the present work is to prepare a nickel catalyst with a metal loading of 5 wt% Ni supported on a SiO 2-C composite, to be used in the liquid-phase glycerol hydrogenolysis reaction. The most active and selective catalyst to 1,2-propylene glycol (1,2-PG) was Ni/SC-095, which presented surface acidity fundamentally represented by the presence of carboxylic groups which promoted the CeO cleavage reactions of the glycerol primary carbon to produce acetol, and subsequently by hydrogenation to produce 1,2-PG. Concerning the selection of operating conditions, the influence of the most relevant variables of the process were analyzed, i.e., temperature (220-260°C), glycerol concentration (30-65%), and hydrogen partial pressure (0-4 MPa). The best result was obtained at 260°C with 30 wt% glycerol, 6 h on reaction and a hydrogen partial pressure of 2 MPa. Under these conditions, selectivities of 77% towards 1,2-PG and 3% to acetol were obtained, with 56% of conversion. It was demonstrated that there are no important structural changes through the characterization of the used samples. Both the SC-095 support and the Ni/SC-095 catalyst maintained their BET surface area. By XRD and TEM, there could be a slight increase in particle size, which would indicate good resistance to sintering against the severe hydrothermal conditions of this reaction.
Applied Catalysis A: General, 2017
In previous studies, we prepared Ni catalysts supported on a silica-carbon composite which is sel... more In previous studies, we prepared Ni catalysts supported on a silica-carbon composite which is selective for obtaining 1,2-propylene glycol (1,2-PG). In order to improve the activity levels of this catalyst, in the present work we propose to modify the catalyst formulation by means of two strategies: on the one hand, to modify the acidity of the catalyst through the functionalization of the carbon support and, on the other hand, to modify the metallic phase by the addition of Zn from a controlled preparation technique (Surface Organometallic Chemistry on Metals), which allows the selective addition of small amounts of modifier on the metallic particles. The functionalization of the SC support at 80°C employing HNO 3 at 60 wt% as oxidizing agent allowed increasing the number of surface acid sites that provide Lewis-type acidity without loss of specific surface area. The addition of 1.1-1.8 wt% of Zn (which corresponds to catalysts NiZn0.2/SC and NiZn0.32/SC) generates the formation of an active site composed of an α-NiZn alloy responsible for the increase in activity. When the addition of Zn is 2.8 wt% (which corresponds to catalyst NiZn0.5/SC), the generation of a new tetragonal phase of β 1-NiZn would cause the decrease of catalytic activity. These results indicate that the Zn addition has a more significant effect upon the activity and selectivity on the CeO bond cleavage reactions than the effect of the support acidity upon the dehydration activity.
Catalysts, 2016
In this work, structural and morphological properties of SiO 2-C composite material to be used as... more In this work, structural and morphological properties of SiO 2-C composite material to be used as support for catalysts in the conversion of biomass-derived oxygenated hydrocarbons, such as glycerol, were investigated in liquid water under various temperatures conditions. The results show that this material does not lose surface area, and the hot liquid water does not generate changes in the structure. Neither change in relative concentrations of oxygen functional groups nor in Si/C ratio due to hydrothermal treatment was revealed by X-ray photoelectron spectroscopy (XPS) analysis. Raman analysis showed that the material is made of a disordered graphitic structure in an amorphous silica matrix, which remains stable after hydrothermal treatment. Results of the hydrogenolysis of glycerol using a Ru/SiO 2-C catalyst indicate that the support gives more stability to the active phase than a Ru/SiO 2 consisting of commercial silica.
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Papers by Martin Nicolas Gatti