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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.

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.

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.

Isobaric vapor–liquid equilibria (VLE) for the ternary system acetone + methanol +1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) as well as the two solvent + IL binary systems have been obtained at 100 kPa using a recirculating still. The addition of [emim][DCA] to the solvent mixture produced a salting-out effect greater than that produced by other ionic liquids, showing that this ionic liquid is, until now, the best IL tested as an entrainer for the extractive distillation of the acetone + methanol mixtures, causing the azeotrope to disappear for an ionic liquid mole fraction as low as 0.031, at 100 kPa. This behavior can be explained on the basis of the influence of the IL concentration on the activity coefficient of each solvent in the binary mixtures. The electrolyte nonrandom two-liquid (NRTL) model was used for fitting successfully the experimental data.

Isobaric vapor–liquid equilibria (VLE) for the 1-propanol + 1-butyl-3-ethylimidazolium trifluoromethanesulfonate ([beim][triflate]), water + [beim][triflate], 1-propanol + 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ([bmpyr][triflate]), and water + [bmpyr][triflate] binary systems, as well as the VLE for the 1-propanol + water + [beim][triflate] and 1-propanol + water + [bmpyr][triflate] ternary systems have been obtained at 100 kPa using a recirculating still. The salting-out effect on the 1-propanol produced by the [bmpyr][triflate] was stronger than that produced by the [beim][triflate], although for the IL concentrations used in this study the effect was not enough to break the azeotrope, unlike of that produced by the 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]). The electrolyte nonrandom two-liquid (NRTL) model was used for fitting successfully the experimental data.

Refractive indices were determined for four different ionic liquid + water binary systems, from (288.15 to 338.15) K, and covering the entire composition range. The four ionic liquids used were 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 3-butyl-1-ethylimidazolium trifluoromethanesulfonate, 3-butyl-1-methylimidazolium trifluoromethanesulfonate, and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, all of them being completely miscible in water. From the experimental data, deviations in refractive indices, defined on a volume fraction basis, have been calculated and fitted to an extended version of the Redlich–Kister equation. The behavior of the deviations in refractive indices with composition, temperature, and size of the anion of ionic liquid has been analyzed and compared with that presented by the excess molar volume of the same systems.

Isobaric vapor–liquid equilibria (VLE) for the binary systems acetone + 1-butyl-3-ethylimidazolium trifluoromethanesulfonate ([beim][triflate]), methanol + [beim][triflate], acetone + 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ([bmpyr][triflate]), and methanol + [bmpyr][triflate] as well as the VLE for the acetone + methanol + [beim][triflate] and acetone + methanol + [bmpyr][triflate] ternary systems have been obtained at 100 kPa using a recirculating still. The addition of both ionic liquids to the solvent mixtures produced an important salting-out effect, and the azeotrope tended to disappear for small amounts of ionic liquid. The experimental binary data sets were independently fitted with the electrolyte nonrandom two-liquid (NRTL) model, and the parameters of the Mock's model were estimated for each binary system. These parameters were used to predict the ternary VLE, which agreed very well with the experimental ones.

Isobaric vapor−liquid equilibria for the binary systems 1-propanol + water, 1-propanol + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]), and water + [emim][triflate] as well as the vapor−liquid equilibria for the 1-propanol + water + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. Electrolyte NRTL fitting parameters for the 1-propanol + water and water + [emim][triflate] systems were calculated. The measured ternary data were correlated using Mock’s electrolyte NRTL model which reproduces reasonably well the experimental values. The results show that the addition of [emim][triflate] to 1-propanol + water produced an important salting-out effect, and the model predicts that at 100 kPa the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.34.

The speed of sound and density of mixtures of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]) with methanol, ethanol, 1-propanol, and water, as well as of the pure components have been experimentally measured over the whole range of compositions at T = (278.15 to 338.15) K and atmospheric pressure. From these experimental data, the excess molar volume, excess isentropic compressibility, and excess speed of sound have been calculated and fitted to an extended version of the Redlich−Kister equation, which takes into account the dependence on composition and temperature simultaneously. The Prigogine−Flory−Patterson theory has also been used to explain the behavior of these systems.

Densities of 1-butyl-3-methylimidazolium octylsulfate ([bmim][OcOSO3]) solutions in water and 1-propanol have been measured with an oscillating-tube densimeter at temperatures from 278.15 K to 328.15 K. From these densities, apparent molar volumes Vϕ of [bmim][OcOSO3] in both solvents have been calculated, and its dependence on the molality has been treated with the Redlich and Meyer equation. Debye–Huckel limiting slopes for 1-propanol at working temperatures have been calculated, and apparent molar volumes of [bmim][OcOSO3] at infinite dilution V ϕ ∘ in both solvents have been evaluated. The partial molar volume at infinite dilution of [bmim][OcOSO3] in water is higher than in 1-propanol and augments when the temperature augments. On the other hand, the partial molar volume at infinite dilution of [bmim][OcOSO3] in 1-propanol decreases when the temperature augments.

In order to increase ethene and propene, naphtha steam catalytic cracking has been considered. The cracking of C 5-C 12 n-alkanes with ZSM-5 has been studied in absence and in presence of steam and the influence of the operation variables was studied. Irreversible catalyst deactivation by dealumination also occurs in the reactor when the cracking is carried out in the presence of steam. To diminish steam deactivation, the influence of zeolite Si/Al framework and a postsynthesis treatment by phosphorous have been studied and optimized. Much more stable catalyst can be achieved that result in an increase in activity without penalty for production of ethene and propene., Financial support by the Ministerio de Ciencia e Innovacion of Spain (MICINN) (Project MAT2006-14274-C02-01) and by Consolider-Ingenio 2010 (Project MULTICAT) is gratefully acknowledged.