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10 figures y 4 tables.-- Supplementary information available., The growing demand of energy needs the search for alternative energy sources different to fossil fuels. The use of biomass as energy source is one of the most studied, because there are high value products that can be produced from biomass. One of these products is γ-valerolactone, that can be obtained from furfural, which is a biomass derived product. To transform furfural into γ-valerolactone is necessary a bifunctional catalyst and a hydrogen source. In this work, γ-valerolactone was obtained from furfural using 2-propanol as solvent and as hydrogen donor on Zr supported on sepiolite catalysts. It was demonstrated that sepiolite, which is a cheap material, can be used to develop efficient catalysts to produce high yields to γ-valerolactone from furfural in one-pot. The catalysts that presented the highest yield to γ-valerolactone were the ones with intermediate Zr-content (9–17 wt% ZrO2). The highest TOFs have been obtained by those catalysts with Zr-loading up to 9 wt% ZrO2, in which the ZrO2 nanoparticles are well dispersed on the support and no formation of large clusters of ZrO2 has been observed. Lewis and Brønsted acid sites are essential in the catalysts to produce the reactions to transform furfural into γ-valerolactone in one-pot, although in the present work, low concentration of Brønsted acid sites were observed in the catalysts. A possible positive role of basic sites to promote some intermediate steps has been also proposed. The catalytic results obtained are in the order of catalysts with Zr supported on zeolitic supports., A.G. thanks MINECO for the pre-doctoral grant (PRE2018-085211). This work was funded by the MAT2017-84118-C2-1-R, MAT2017-84118-C2-2-R, MCIN/AEI/10.13039/501100011033/projects and FEDER Una manera de hacer Europa. Authors thank the electron microscopy CAI center of UCM. Authors also thank the Generalitat Valenciana for CIAICO/2021/094.

The study for the production of gamma-valerolactone from furfural in one-pot has been carried out using ZrO2 supported on silica spheres. The catalysts synthesized were characterized by XRD, UV-vis, HR-TEM, N-2 adsorption, IR, pyridine adsorption-IR and NH3-TPD in order to determine their physicochemical characteristics. Both, Lewis and Bronsted acid sites are necessary to produce gamma-valerolactone from furfural, because they are involved in different steps of the reaction. Accordingly, a reaction mechanism has been proposed. Lewis acid sites of ZrO2 interacting with the -OH surface groups of the siliceous spheres can generate Bronsted acid sites in the supported Zr catalysts, which are absent in both pure ZrO2 and the silica spheres. Then, by controlling the amount of Zr in the supported catalysts, the relative amount of Lewis and Bronsted acid sites can be optimized to obtain the highest yields to gamma-valerolactone. The Zr-loading of the optimal supported catalyst was ca. 7 wt% Zr, which reached a gamma-valerolactone yield of 72.4 % after 8 h at 180 C using 2-propanol as a solvent and hydrogen donor.

1 scheme, 2 tables, 7 figures.-- Supplementary material available., In the present article, gamma-valerolactone has been obtained from levulinic acid with a yield exceeding 25% using very mild conditions without feeding hydrogen (30 degrees C, atmospheric pressure, water as the hydrogen source). The overall reaction conducted is a two-step process: first, a redox reaction involving the oxidation of metallic Zn to ZnO for in situ hydrogen production through the water splitting reaction and, second, a catalytic reaction involving Ni-supported catalysts for the production of gamma-valerolactone from levulinic acid. Ni active sites have been supported on sepiolite, an abundant and cheap material. The nickel particle size has been demonstrated to be a parameter of paramount importance determining the catalytic activity, since the best catalytic performance is obtained with the smallest Ni nanoparticles. This combination of Zn and Ni supported on sepiolite shows a good catalytic stability after three catalytic runs., Authors from UCM thank MINECO (MAT2017-84118-C2-2-R project) and UCM CAI center of EM. Authors from UV thank MINECO (MAT2017-84118-C2-1-R project) and FEDER for funding. A. G. thanks MINECO for the pre-doctoral grant.

13 figures, 7 tables.-- © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0, Ni-based catalysts supported on sepiolite were synthesized by different preparation procedures for the production of γ-valerolactone from levulinic acid and its esters (methyl levulinate and ethyl levulinate). The optimal performance was related to the formation of tiny nickel particles. Interestingly, the reaction conditions significantly influence the reactivity of the substrates. The catalytic performance of the optimal Ni/sepiolite catalyst was compared with two catalysts of ruthenium (supported on γ-alumina or sepiolite). In all cases, the production of γ-valerolactone depends on both the substrate employed and the reaction media. Overall, the preferred reaction media using the Ni-catalyst is 2-propanol whereas pressurized hydrogen in water is the best alternative for Ru-catalysts. In both cases, a reasonable stability has been observed after 3 cycles. Finally, the use of metallic Zn in an aqueous medium to provide hydrogen could not be considered as an appropriate option due to the lack of a stable behaviour., Authors from UCM thank MINECO(MAT2017-84118-C2-2-R project) and UCM CAI center of EM. Authors from UV thank MINECO (MAT2017-84118-C2-1-R project) and FEDER for funding. A.G. thanks MINECO for the pre-doctoral grant.

Isobaric vapor–liquid equilibria for the 1-propanol + 1-ethyl-3-methylimidazolium dicyanamide ([emim [DCA] binary system and for the 1-propanol + water + [emim] [DCA] ternary system have been obtained at 100 kPa using a recirculating still. The electrolyte nonrandom two-liquid (e-NRTL) model was used for fitting successfully the experimental data. The effect of [emim][DCA] on the 1-propanol + water system has been compared with that produced by other ionic liquids reported in the literature. From the results, [emim][DCA] appears as a potential entrainer for the extractive distillation of this solvent mixture, causing the azeotrope to disappear at 100 kPa when the ionic liquid mole fraction is greater than 0.33.

Isobaric vapor–liquid equilibria for the binary systems 2-propanol + water, 2-propanol + 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]), and water + [emim][DCA] as well as the vapor–liquid equilibria for the 2-propanol + water + [emim][DCA] ternary system have been obtained at 100 kPa using a recirculating still. The electrolyte nonrandom two-liquid (e-NRTL) model was used for fitting successfully the experimental data. The effect of [emim][DCA] on the 2-propanol + water system has been compared with that produced by other ionic liquids reported in the literature. From the results, [emim][DCA] appears as a good entrainer for the extractive distillation of this solvent mixture, causing the azeotrope to disappear at 100 kPa when the ionic liquid mole fraction is greater than 0.085.

[EN] There is a need for on-purpose propene production technologies beyond energy-intensive steam cracking. Hexene is a compound with limited value that can be found in several streams in the refinery and can readily crack on zeolites at lower temperatures and shorter contact times than those used for cracking alkanes. Cracking over ZSM-5 zeolite yields high selectivity to light olefins. These results are improved by Theta-1 zeolite, which can yield a remarkable propene molar selectivity of 180% (90 wt%) at 90% conversion, close to the maximum thermodynamic yield. Moreover, crystal engineering allowed its TOF to increase by more than 50%. Based on these results we also identified some prospective applications of Theta-1 zeolite as a catalyst for an integrated process directed to maximize propene., Financial support by the Ministerio de Economia y Competitividad of Spain (MINECO) through the project CTQ2015-70126-R is gratefully acknowledged. V. Blay thanks the support from the Valencian Ministry of Education. The authors thank Costa Lau for creating the graphical abstract.

Densities, speeds of sound, viscosities and refractive indices of two binary systems 1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4] + methanol and 1-ethyl-3-methylimidazolium tetrafluoroborate [emim][BF4] + methanol, as well as of all pure components, have been measured covering the whole range of compositions at T = (278.15 to 318.15) K and p = 101 kPa. From this data, excess molar volumes, excess isentropic compressibilities, viscosity deviations and refractive index deviations were calculated and fitted to extended versions of the Redlich–Kister equation. Estimated coefficients of these equations taking into account the dependence on composition and temperature simultaneously were also presented.