Examinando por Autor "Mariscal, Rafael"

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Defective UiO-66(Zr) as an efficient catalyst for the synthesis of bio jet-fuel precursors via aldol condensation of furfural and MIBK
(Elsevier, 2021-07-23) de la Flor, Daniel; López-Aguado, Clara; Paniagua, Marta; Morales, Gabriel; Mariscal, Rafael; Melero, Juan Antonio
The production of jet-fuel precursors from furfural (FUR) via aldol-condensation with methyl-isobutyl ketone (MIBK) over a defective UiO-66(Zr) catalyst is presented. The resultant C11 adduct (FuMe) would allow the selective production of branched alkanes in the range of jet fuel via a subsequent hydrogenation/hydrodeoxygenation process. The catalyst is prepared using formic acid as modulator, leading to the incorporation of defects on the microcrystalline structure of the metalorganic framework (MOF) material, which dramatically boosts the catalytic performance in this transformation. Thus, the benchmarking with different commercial solid acid catalysts and Zr-based heterogeneous catalysts has identified the defective MOF, UiO-66(Zr)-FA, as clearly superior. An extensive characterization of the modified catalyst by means of X-ray diffraction (XRD), argon adsorption isotherm, thermogravimetry (TGA), acid titration, X-ray photoelectron spectroscopy (XPS), and diffuse reflectance infrared Fourier transform (DRIFT) of adsorbed deuterated acetonitrile, has confirmed the incorporation of missinglinker and missing-node defects within the structure, enabling to explain the enhancement in the catalytic process. The analysis of the reaction kinetics, together with the optimization of the reaction conditions by means of a response surface methodology (allowing predicting the behaviour of the catalytic system under very different conditions) have identified the temperature as the most relevant parameter affecting the selectivity to FuMe. Thus, under the optimized reaction conditions (130 C; 4 h; FUR/Cat = 2; MIBK/FUR = 4), outstanding total FUR conversion and FuMe selectivity (~100%) can be achieved. However, the catalyst gets progressively deactivated in successive catalytic runs under the studied reaction conditions, which is attributed to the formation of organic deposits coming from furfural side reactions.
Efficient Conversion of Glucose to Methyl Lactate with Sn-USY: Retro-aldol Activity Promotion by Controlled Ion Exchange
(ACS, 2022) Jimenez-Martin, Jose M.; Orozco-Saumell, Ana; Hernando, Héctor; Linares, María; Mariscal, Rafael; López Granados, Manuel; García, Alicia; Iglesias, Jose
Sn-USY materials have been prepared through an optimized post-synthetic catalytic metalation procedure. These zeolites displayed, upon ion exchange with alkaline metals, an outstanding activity in the direct transformation of glucose into methyl lactate, yielding more than 70% of the starting glucose as the target product, and an overall combined retro-aldol condensation product yield above 95% in a short reaction time (<4 h). This outstanding catalytic performance is ascribed to the neutralization of Brønsted acid sites, the consequent depression of side reactions, and a higher population of tin open sites in the ion-exchanged Sn-USY zeolites. Reusability tests evidenced some loss of catalytic activity, partially caused by the closing of tin sites, although the use of small amounts of water in the reaction media demonstrated that this deactivation mechanism can be, at least, partially alleviated.
Understanding the role of Al/Zr ratio in Zr-Al-Beta zeolite: Towards the one-pot production of GVL from glucose
(Elsevier, 2021-04-07) Paniagua, Marta; Morales, Gabriel; Melero, Juan Antonio; Iglesias, Jose; López-Aguado, Clara; Vidal, Nora; Mariscal, Rafael; López-Granados, Manuel; Martínez-Salazar, Irene
The direct one-pot transformation of glucose into γ-valerolactone (GVL) can be accomplished by means of a cascade of reactions in which Brønsted acid-catalyzed transformations are combined with catalytic transfer hydrogenation (CTH) by using 2-propanol as sacrificial alcohol, avoiding the use of high-pressure hydrogen. Catalysts containing Zr Lewis acid sites have been successfully applied in CTH reactions while the acid-driven transformations can be preferentially promoted by Brønsted Al-related acidity. Here, we present the combination of Zr and Al as active sites within a BEA zeolite structure as catalyst, with the possibility of adjusting the Al/ Zr ratio from ∞ (commercial H-Beta) to 0 (aluminium-free Zr-Beta), which show a scale of Brønsted/Lewis acid sites ratios. The Al/Zr ratio has a strong impact on the products distribution. As the Zr content increases, higher amount of GVL is obtained, leading to a maximum over the catalyst with high amount of Zr and low content of Al acid sites (Al/Zr = 0.2). An increase of reaction temperature, as well as reaction time, allows an enhancement of yields towards the desired products, leading to a maximum yield towards GVL of 24 mol% over Zr-Al-Beta (2.0), and a maximum yield towards isopropyl lactate of 26 mol% over Zr-Beta at 190 ◦C.