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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.

In this work, densities and sound velocities of three ionic liquids, 3-butyl-1-ethylimidazolium trifluoromethanesulfonate, 3-butyl-1-methylimidazolium trifluoromethanesulfonate, and 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate, and their binary mixtures with water have been obtained at p = (101 ± 2) kPa and T = (278.15 to 338.15) K, covering the whole range of concentration. The isentropic compressibility and molar isentropic compression of pure components and mixtures have been calculated using the Newton–Laplace equation. Moreover, the excess molar volume and excess molar isentropic compression of mixtures have been then determined, and they have been fitted to temperature and composition by an extended Redlich–Kister equation. Optimal fitting parameters have been reported.

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 binary systems ethanol + 1-ethyl-3-methylimidazolium dicyanamide ([emim][DCA]) and water + [emim][DCA] as well as the VLE for the ternary system ethanol + water + [emim][DCA] have been obtained at 100 kPa using a recirculating still. The effect of [emim][DCA] on the ethanol + water system has been compared with that produced by another ionic liquid reported in the literature on the basis of the variation of solvent activity coefficients in ionic liquid (IL) + molecular solvent binary systems. From the results, [emim][DCA] appears as one of the best entrainers for the extractive distillation of the ethanol + water mixtures, causing the azeotrope to disappear at 100 kPa for ionic liquid mole fractions as low as 0.019. The experimental data were fitted with the Mock's electrolyte nonrandom two-liquid (NRTL) model, with a good agreement.

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 (VLE) for the ethanol + water + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. The ethanol + water binary system was also obtained. Furthermore, data were simulated with the Mock’s electrolyte nonrandom two-liquid (NRTL) model, using the solvent−solvent interaction parameters obtained from VLE data of the ethanol + water system and taking the solvent−ionic liquid (IL) interaction parameters for the other binary systems from previous works. The agreement between experimental and calculated data is very good, showing the predictive capacity of the model. The addition of [emim][triflate] produces the disappearance of the ethanol + water azeotrope when the mole fraction of ionic liquid in the liquid phase is greater than 0.023 at 100 kPa. The effect of [emim][triflate] on the ethanol + water system has been compared with that produced by other ionic liquids reported in the literature.

Isobaric vapor−liquid equilibria for the binary system chloroform + methanol as well as the vapor−liquid equilibria for the chloroform + methanol + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. The ternary ionic liquid (IL) system presents an immiscibility zone at high chloroform composition, which increases with the temperature. Liquid−liquid equilibria for this system have also been determined. The measured ternary vapor−liquid equilibrium data were correlated using the Mock’s electrolyte nonrandom two-liquid (NRTL) model which reproduces reasonably well the experimental values and predicts the total disappearance of the azeotrope when the mole fraction of ionic liquid in the liquid phase is 0.25. The immiscibility does not affect the use of [emim][triflate] as the entrainer for the complete chloroform + methanol separation.

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.

Isobaric vapor−liquid equilibria for the binary systems ethyl acetate + ethanol, ethyl acetate + 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]), and ethanol + [emim][triflate] as well as the vapor−liquid equilibria for the ethyl acetate + ethanol + [emim][triflate] ternary system have been obtained at 100 kPa using a recirculating still. NRTL fitting parameters for the ethyl acetate + ethanol and ethanol + [emim][triflate] systems were calculated. The measured ternary data were correlated using the Mock electrolyte NRTL model, which reproduces reasonably well the experimental values. The results suggest that the addition of [emim][triflate] to the ethyl acetate + ethanol mixture produced an important salting-out effect, and the azeotrope disappears when the mole fraction of ionic liquid in the liquid phase is greater than 0.20.

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.

Isobaric vapor−liquid equilibria have been obtained for the systems tetrachloroethylene + 1-pentanol, tetrachloroethylene + 3-methyl-1-butanol, and tetrachloroethylene + 2-methyl-1-butanol, using a...

Isobaric vapor−liquid equilibria were obtained for 1-butanol + chlorobenzene and for 2-butanol + chlorobenzene systems at 20 and 100 kPa using a dynamic still. The experimental error in temperature was ±0.1 K, in pressure ±0.01 kPa and ±0.1 kPa for the experiments carried out at 20 and 100 kPa, respectively, and in liquid and vapor composition ±0.001. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were correlated with the Wilson equation.

Isobaric vapor−liquid equilibria were obtained for tetrachloroethylene + 1-propanol and +2-propanol systems at 20 and 100 kPa using a dynamic still. The experimental error in temperature was ±0.1 K, in pressure ±0.01 kPa and ±0.1 kPa for the experiments carried out at 20 and 100 kPa, respectively, and in liquid and vapor composition 0.001. The two systems satisfy the point-to-point thermodynamic consistency test. Both systems show a positive deviation from ideality. The data were well correlated with the Wilson equation.

Controlling the location of acid sites in zeolites can have a great effect on catalysis. In this work we face the objective of directing the location of Al into the 10R channels of ZSM-5 by taking advantage of the structural preference of B to occupy certain positions at the channel intersections, as suggested by theoretical calculations. The synthesis of B-Al-ZSM-5 zeolites with variable Si/Al and Si/B ratios, followed by B removal in a postsynthesis treatment, produces ZSM-5 samples enriched in Al occupying positions at 10R channels. The location of the acid sites is determined on the basis of the product distribution of 1-hexene cracking as a test reaction. The higher selectivity to propene and lower C /C ratio in the samples synthesized with B and subsequently deboronated can be related to a larger concentration of acid sites in 10R channels, where monomolecular cracking occurs. Finally, several ZSM-5 samples have been tested in the methanol to propene reaction, and those synthesized through the B-assisted method show longer catalytic lifetime, higher propene yield, and lower yield of alkanes and aromatics., This work was supported by the European Union through ERC-AdG-2014-671093 (SynCatMatch) and the Spanish Government-MINECO through ‘‘Severo Ochoa” (SEV-2016-0683) and CTQ2015-70126-R. The Electron Microscopy Service of the UPV is acknowledged for their help in sample characterization. Red Española de Supercomputación (RES) and Centre de Càlcul de la Universitat de Valencia are gratefully acknowledged for computational resources and technical support. C.L. acknowledges the China Scholarship Council (CSC) for a Ph.D. fellowship.

n-Decane, n-dodecane, and n-tetradecane have been cracked at very short time on stream on ZSM-5, BETA, and USY zeolites. It is shown that different reaction schemes can be used to explain the initial selectivity values obtained for the different products. In all cases an “uncertainty band” was found which makes it impossible to determine with accuracy the separated contribution of the mono- and bimolecular cracking to the overall cracking. Nevertheless, it has been possible to establish the selectivities for the hydrogen transfer reactions. Finally, the influence of the zeolite structure, chain length, time on stream, and level of conversion on the product distribution and the extent of the reactions involved has been studied.

Vapor−liquid equilibria were measured for binary systems of octane + decane, decane + dodecane, and octane + dodecane at 20.00 kPa using a recirculating still. The results are thermodynamically consistent according to the point-to-point consistency test, and deviation from ideal behavior is small for all systems.