0000000000046730
AUTHOR
Francisco J. Llopis
Density, Speed of Sound, and Refractive Index of 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate with Acetone, Methyl Acetate, and Ethyl Acetate at Temperatures from (278.15 to 328.15) K
Densities, speeds of sound, and refractive indices of the binary mixtures of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]) with acetone, methyl acetate, and ethyl acetate were experimentally measured over the whole range of compositions at T = (278.15 to 328.15) K and a pressure of 0.1 MPa. From these experimental data, excess molar volumes, excess isentropic compressibilities, molar refractions, and deviations in refractive indices 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 been used to specula…
Volumetric and Acoustic Properties of Aqueous Solutions of Trifluoromethanesulfonate-Based Ionic Liquids at Several Temperatures
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 …
Vapor–liquid equilibrium of binary mixtures of trichloroethylene with 1-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol at 100 kPa
Abstract Isobaric vapor–liquid equilibria (VLE) have been obtained for the systems trichloroethylene+1-pentanol, trichloroethylene+2-methyl-1-butanol and trichloroethylene+3-methyl-1-butanol at 100 kPa using a dynamic still. The experimental error in temperature is ±0.1 K, in pressure ±0.1 kPa, and in the liquid and vapor mole fraction ±0.001. The three systems satisfy the point-to-point thermodynamic consistency test. All the systems show positive deviations from ideality. The data have been correlated with the Margules, van Laar, Wilson, NRTL and UNIQUAC equations.
On the Mechanism of Xylene Isomerization and its Limitations as Reaction Test for Solid Acid Catalysts
The kinetics of the gas-phase isomerization of m-xylene, over a series of ultraestable Y zeolites, has been studied in a fixed-bed flow reactor under initial conditions. Using deuterated p-xylene as reactant it has been seen that more than 20% of the m- and o-xylene obtained, are formed via a bimolecular mechanism. The relative proportion of uni- to bimolecular mechanism depends on the zeolite composition. The relation between the turnover number, calculated from the kinetic rate constant for the unimolecular mechanism, and the framework Al content of the zeolite, was coincident with the topological zeolite model. Besides, the values of the adsorption constants indicate that dealumination h…
Phase equilibria and variation of the azeotropic composition with pressure for binary mixtures of 1-propanol + chlorobenzene and 1-butanol + chlorobenzene
Abstract Isobaric vapor-liquid equilibria were obtained for the systems 1-propanol + chlorobenzene and 1-butanol + chlorobenzene at 200 and 300 kPa using a dynamic still. The mole fraction of the alcohol in the azeotropic point increases with pressure and for the 1-propanol + chlorobenzene system at 300 kPa, the azeotrope has disappeared. 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 Margules, van Laar, Wilson. NRTL and UNIQUAC equations.
Isobaric vapor-liquid equilibrium of binary mixtures of 1-propanol + chlorobenzene and 2-propanol + chlorobenzene
Abstract Isobaric vapor-liquid equilibria were obtained for the system 1-propanol + chlorobenzene at 20 and 100 kPa and for the system 2-propanol + chlorobenzene at 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 the liquid and vapor mole fraction 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 Margules, Van Laar, Wilson, NRTL and UNIQUAC equations.
Vapor–liquid equilibrium of binary mixtures of chlorobenzene with 3-methyl-1-butanol, 3-methyl-2-butanol and 2-methyl-2-butanol, at 100 kPa
Abstract Isobaric vapor–liquid equilibria have been obtained for the systems 3-methyl-1-butanol+chlorobenzene, 3-methyl-2-butanol+chlorobenzene and 2-methyl-2-butanol+chlorobenzene at 100 kPa, using a dynamic still. The experimental error in temperature is ±0.1 K, in pressure ±0.1 kPa, and in the liquid and vapor mole fraction ±0.001. The three systems satisfy the point-to-point thermodynamic consistency test. All the systems show positive deviations from ideality. The data have been correlated with the Margules, Van Laar, Wilson, NRTL and UNIQUAC equations.
Influence of Some Ionic Liquids Containing the Trifluoromethanesulfonate Anion on the Vapor–Liquid Equilibria of the Acetone + Methanol System
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 independe…
Non-oxidative dehydroaromatization of methane:an effective reaction regeneration cyclic operation for catalyst life extension
[EN] Non-oxidative methane aromatization is an attractive direct route for producing higher hydrocarbons. It is highly selective to benzene despite the low conversion due to thermodynamic limitations, and Mo/H-ZSM-5, the first catalyst proposed for this reaction, is still considered as one of the most adequate. The major problem of this process is the severe catalyst deactivation due to the rapid build-up of carbonaceous deposits on the catalysts. Here we present an effective regeneration procedure that extends the life of Mo/zeolite based catalysts by combining reaction periods of 1.5 h with 0.5 h regeneration steps in a continuous cyclic mode and methane activation after each regeneration…
Increasing the stability of the Ge-containing extra-large pore ITQ-33 zeolite by post-synthetic acid treatments
[EN] Extra-large pore ITQ-33 zeolite (ITT, 18 x 10 x 10-rings) is a very promising catalyst for the catalytic cracking of gasoil but, unfortunately, this material shows a limited hydrothermal stability due to the large germanium content present in the ITQ-33 structure. Taking this into account, the Ge-containing ITQ-33 has been post synthetically modified using different acid procedures with the aim of studying the effect of these treatments on the overall hydrothermal stability of this extra-large pore zeolite. In this sense, the as-prepared ITQ-33 has been treated with different HCl solutions in ethanol (from 0.1 to 1 M), containing also tetraethylorthosilicate (TEOS) as silicon precursor…
Isobaric Vapor–Liquid Equilibria for the Extractive Distillation of Ethanol + Water Mixtures Using 1-Ethyl-3-methylimidazolium Dicyanamide
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…
Vapor−Liquid Equilibrium of Binary Mixtures of Tetrachloroethylene with 1-Pentanol, 3-Methyl-1-butanol, and 2-Methyl-1-butanol
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...
Refractive Indices and Deviations in Refractive Indices for Binary Mixtures of 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate with Methanol, Ethanol, 1-Propanol, and 2-Propanol at Several Temperatures
Refractive indices of the binary mixtures of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim][triflate]) with methanol, ethanol, 1-propanol, and 2-propanol were experimentally measured over the whole range of compositions at T = (288.15 to 338.15) K and atmospheric pressure. From the experimental data, deviations in refractive indices 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. This dependence has been discussed. The deviations are always positive, and their extent follows the sequence methanol > ethanol > 2-propanol > 1-propanol, increasing when tem…
A New Aluminosilicate Molecular Sieve with a System of Pores between Those of ZSM-5 and Beta Zeolite
[EN] A new aluminosilicate zeolite (ITQ-39) has been synthesized. This is an extensively faulted structure with very small domains that makes the structure elucidation very difficult. However, a combination of adsorption spectroscopy and reactivity studies with selected probe molecules suggests that the pore structure of ITQ-39 is related to that of Beta zeolite, with a three-directional channel system with large pores (12-MR), but with an effective pore diameter between those of Beta and ZSM-5, or a three-directional channel system with interconnected large (12-MR) and medium pores (10-MR). The pore topology of ITQ-39 is very attractive for catalysis and shows excellent results for the pre…
Volumetric properties, viscosities and refractive indices of binary liquid mixtures of tetrafluoroborate-based ionic liquids with methanol at several temperatures
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 simult…
Isobaric vapor-liquid equilibria for the 1-propanol + water + 1-ethyl-3-methylimidazolium dicyanamide system at 100 kPa
Abstract 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 …
Isobaric vapor-liquid equilibria for the extractive distillation of 2-propanol + water mixtures using 1-ethyl-3-methylimidazolium dicyanamide ionic liquid
Abstract 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 mixtur…
Xylene isomerization and aromatic alkylation in zeolites NU-87, SSZ-33, β, and ZSM-5: molecular dynamics and catalytic studies
The unique pore topology of zeolite NU-87, with 10-membered ring (MR) channels intersected by perpendicular 12-MR cavities, can offer new opportunities for alkylaromatics isomerization, as well as for aromatics alkylation. The catalytic performance has been studied for meta-xylene isomerization and disproportionation, as well as toluene alkylation with methanol, ethanol, propanol, and isopropanol. Product distribution was interpreted on the basis of pore topology and compared to zeolites with 12-MR (β), 10- and 12-MR (SSZ-33), and 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for the location of bulky intermediates and/or products, and also traps the molecules, allowing…
Influence of Pore-Volume Topology of Zeolite ITQ-7 in Alkylation and Isomerization of Aromatic Compounds
The void structure of zeolite ITQ-7 (ISV structure) is discussed on the basis of catalytic reaction tests. The isomerization and disproportionation of meta-xylene, and the alkylation of benzene or toluene with either ethanol or isopropanol, on the acidic zeolite have been used as model reactions. The dimensions of its three-dimensional system of channels, with pores between 6.1 and 6.3 A and with lower tortuosity than those of beta zeolite, favor higher ratios of isomerization to disproportionation of meta-xylene, and of mono- to dialkylated products and iso- to n-propylbenzene during alkylation of benzene. These effects are enhanced with a partially coked ITQ-7.
Easy Method for the Transformation of Levulinic Acid into Gamma-Valerolactone Using a Nickel Catalyst Derived from Nanocasted Nickel Oxide
Different nickel catalysts have been tested for the transformation of levulinic acid into &gamma
Structure-reactivity relationship for aromatics transalkylation and isomerization process with TNU-9, MCM-22 and ZSM-5 zeolites, and their industrial implications
[EN] TNU-9 is a medium pore zeolite with a complex tridimensional channel system. Its catalytic properties have been studied in some reactions that involve the BTX fraction, such as benzene and toluene alkylation with methanol, ethanol or isopropanol. These reactions use in practice medium pore zeolites such as ZSM-5 (MFI) or MCM-22 (MWW), and the selectivities obtained with TNU-9 are compared and analyzed from the point of view of the zeolite structure and pore topology, as well as from its possible industrial application. For benzene alkylation to give ethylbenzene (EB), TNU-9 is an active and selective catalyst with selectivities to EB much higher than ZSM-5 and close to those of the ind…
Isomerization and disproportionation of m-xylene in a zeolite with 9- and 10-membered ring pores: Molecular dynamics and catalytic studies
The unique pore topology of zeolite ITQ-13 with 9-membered ring (MR) channels intersected by perpendicular 10-MR channels and larger void space with 10-MR cross-sections was studied for meta-xylene isomerization and disproportionation. Product distribution was interpreted on the basis of pore topology and compared with zeolites with 12-MR (β), 10-MR, and intersecting 12-MR cavities (NU-87), as well as 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for bulky intermediates and/or products and also provides room for molecules to drive consecutive reactions toward thermodynamic equilibrium. Channels, on the other hand, allow diffusion without trapping if their free diameters…
Isobaric Vapor−Liquid Equilibrium of Binary Mixtures of 1-Butanol + Chlorobenzene and 2-Butanol + Chlorobenzene at 20 and 100 kPa
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.
Influence of preparation conditions on the catalytic performance of mo/h-zsm-5 for methane dehydroaromatization
[EN] Methane, the main component of natural gas, is an interesting source of chemicals and clean liquid fuels, and a promising alternative raw material to oil. Among the possible direct routes for methane conversion, its aromatization under non-oxidative conditions has received increasing attention, despite the low conversions obtained due to thermodynamic limitations, because of its high selectivity to benzene. Mo/H-ZSM-5, the first bifunctional zeolite-catalyst proposed for this reaction, is still considered as one of the most adequate and has been widely studied. Although the mono- or bifunctional nature of the MDA mechanism is still under debate, it is generally accepted that the Mo spe…
Determination of the Pore Topology of Zeolite IM-5 by Means of Catalytic Test Reactions and Hydrocarbon Adsorption Measurements
Abstract The pore topology of a recently synthesized zeolite IM-5 has been determined by means of catalytic test reactions, i.e., n -decane hydroisomerization–cracking, m -xylene isomerization–disproportionation, n -hexadecane isodewaxing, and adsorption–microcalorimetry of molecules with different sizes and shapes ( n -hexane, toluene, m -xylene, and 1,3,5 trimethylbenzene). It has been found that the channel network consists of a system of unidirectional 10 MR with lobes or side pockets, or crossing 10 membered ring pores with a pore diameter somewhat smaller than those in ZSM-5. This structure offers interesting shape selectivity features for catalytic reactions.
Ultrasonic and Volumetric Properties of 1-Ethyl-3-methylimidazolium Trifluoromethanesulfonate Ionic Liquid with 2-Propanol or Tetrahydrofuran at Several Temperatures
Densities and speeds of sound of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate mixtures with 2-propanol and tetrahydrofuran (THF), as well as of the pure components, have been measured over the whole range of compositions at T = (278.15 to 328.15) K and P = (101 ± 2) kPa. From these experimental data, the excess molar volume, excess speed of sound, and excess isentropic compressibility 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.
Assessing the Electrochemical Performance of Different Nanostructured CeO2 Samples as Anodes for Lithium-Ion Batteries
In this work, six samples of CeO2 are successfully prepared by diverse synthesis routes leading to different microstructures regarding both morphology and particle size. The structural and microstructural characteristics presented by the samples and their influence on the electrochemical response of the prepared anodes are analyzed. In particular, the Ce-CMK3 sample, synthesized from a mesoporous carbon obtained through a CMK3 silica template, displays an enhanced electrochemical response. Thus, capacity values of ~220 mA h g−1 are obtained at a current rate of 0.155 A g−1 after 50 cycles and an excellent cyclability at intermediate current densities. On the other hand, it is observed that …
Refractive Indices and Deviations in Refractive Indices of Trifluoromethanesulfonate-Based Ionic Liquids in Water
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 in…
Influence of layer structure preservation on the catalytic properties of the pillared zeolite MCM-36
MCM-36 is a catalytically active material made by swelling and subsequent pillaring of a layered zeolite precursor, MCM-22(P). However, the swelling procedures lead to significant destruction of layer structure and alteration of framework silicon/aluminum (Si/Al) ratio, which are likely to influence the acidity and catalytic activity of the final materials. We report a milder swelling and pillaring process to prevent such structural destruction. The resulting pillared materials show higher crystallinity and improved retention of the zeolitic layer structure when compared to the ones prepared by the previously reported methods involving more aggressive treatments. Implications of such struct…
Thermophysical properties of binary mixtures of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate ionic liquid with alcohols at several temperatures
Abstract Densities, speeds of sound, and refractive indices for the binary systems made up by 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate and methanol, ethanol, 1-propanol, or 2-propanol, as well as for the pure components, have been measured covering the whole range of compositions at atmospheric pressure and T = (278.15–338.15) K. From densities and speeds of sound, isentropic compressibilities were calculated using the Newton-Laplace equation. Liquid ideal-mixture properties have been defined and calculated, and they have been used to determine excess molar volumes, excess isentropic compressibilities, and deviations in refractive indices. Excess and deviations in properties …
The benefit of multipore zeolites: Catalytic behaviour of zeolites with intersecting channels of different sizes for alkylation reactions
Abstract The catalytic behaviour of two multipore zeolites containing channels of different sizes, SSZ-33 (10 windows × 12 MR) and ITQ-22 (8 × 10 × 12 MR pores), for alkylation of benzene with ethanol and benzene with isopropanol or propylene, has been studied and compared to that of zeolites with intersecting channels of the same size, ZSM-5 (10 × 10 MR channels) and Beta (12 × 12 MR channels), which are industrially used for the above-mentioned process. For the alkylation of benzene with ethanol in gas phase, ITQ-22 behaves like the 10 MR ZSM-5 with respect to ethylbenzene selectivity, while the behaviour of SSZ-33 is close to that of a 12 MR zeolite such as Beta. For the alkylation of be…