EXPERIMENTAL STUDY OF THE SELECTIVE HYDROGENATION OF STEAM CRACKING C2CUT. FRONT END AND TAIL END VARIANTS

Selective hydrogenation is the habitual industrial process to eliminate the most unsaturated hydrocarbons, which are harmful for later applications. In this paper, the kinetics of the selective hydrogenation of a C₂ mixture over two palladium/alumina catalysts with both front end and tail end variants, have been studied. Experiments have been carried out to analyse the influence of temperature, hydrogen/acetylene molar ratio, carbon monoxide content in the feed and hydrocarbon volumetric flow rate on the corresponding conversion and selectivity.

The experiments were performed in an integral plug flow reactor and the integral method was used for the kinetic analysis. The minimization of the objective function was made by the Marquardt algorithm for multiple response and the continuity equation set integrated by fourth order Runge-Kutta technique.

The most adequate models were the power law type for the experimental range. The comparison between experimental and observed values of the acetylene and ethane molar fraction in the hydrocarbon mixture, which are used for minimization, confirm the suitability of the fit.     

Enhancement of activity and selectivity in lipase‐catalyzed transesterification in ionic liquids by the use of additives

BACKGROUND: Seven ionic liquids (ILs) based on 1-alkyl-3-methylimidazolium cation in combination with hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions were tested as reaction media for lipase-catalyzed transesterification in low water conditions. With the aim of improving the activity and/or selectivity of the lipase, various treatments were applied to ionic liquid media such as equilibration with aqueous solutions of salts, NaHCO₃ or Na₂CO₃, or the addition of a catalytic amount of a non-reactive organic base to the reaction mixture, triethylamine. RESULTS: The treated ionic liquids were shown to be excellent media for lipase-catalyzed ester synthesis by transesterification compared with conventional organic solvents, such as n-hexane. All treatments were found to enhance the synthetic activity of the enzyme, the best results being achieved with the addition of triethylamine. The addition of a catalytic amount of this base to the ILs resulted in a significant increase in both the synthetic activity and selectivity values. For instance, the synthetic activity in [emim⁺][TfN₂⁻] was enhanced more than 12 times and the selectivity increased from 86% to 95% when triethylamine was used. CONCLUSION: These treatments could be easy-to-use approaches to improve the efficiency of enzymatic reactions in ionic liquids when the reaction does not proceed smoothly. Copyright © 2007 Society of Chemical Industry     

Experimental study of the tail end selective hydrogenation of steam cracking C2-C3 mixture

Diolefins and alkynes in C₂-C₃ olefins streams can be selectively hydrogenated to produce high-purity mono-olefins for downstream polyolefin production. The aim of this paper is on the experimental study of the tail end selective hydrogenation of a stream cracking C₂-C₃ cut, over two different palladium/alumina catalysts. A series of integral reactor type experiments were performed and the integral method was used for the kinetic analysis. The minimization of the objective function was made by the Marquardt algorithm for multiple response and the continuity equation set integrated by fourth order Runge-Kutta technique. The comparison between experimental and observed values of the acetylene, ethylene, ethane, MAPD, propylene and propane molar fraction in the hydrocarbon mixture, which were used for the minimization, confirm the suitability of the fit.     

Understanding the chemical reaction and mass-transfer phenomena in a recirculating enzymatic membrane reactor for green ester synthesis in ionic liquid/supercritical carbon dioxide biphasic systems

The synthesis of butyl propionate in a recirculating bioreactor in room temperature ionic liquid/supercritical carbon dioxide biphasic systems at 50 °C and 80 bar was studied. In these systems, α-alumina microporous membranes with immobilized Candida antarctica lipase B were coated with four different ionic liquids based on 1-n-alkyl-3-imidazolium cations and hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions. Selectivity increased (reaching >99.5%) when room temperature ionic liquid/supercritical carbon dioxide biphasic systems were used rather than in supercritical carbon dioxide alone. To understand the behaviour of the enzyme and the mass-transfer phenomena in these biphasic systems, the reaction was also carried out in ionic liquids and in ionic liquid/hexane biphasic systems, and the ionic liquid/hexane partition coefficients of the compounds involved in the transesterification reaction were determined. It was observed that the activity in room temperature ionic liquid/supercritical carbon dioxide biphasic systems depends on the effect of the ionic liquid media on the enzyme and the diffusional limitations across the IL-layer around the biocatalyst.     

Production of silk fibroin nanoparticles using ionic liquids and high‐power ultrasounds

Biopolymeric nanoparticles have attracted great research interest in the last few years due to their multiple applications. This article describes how high‐power ultrasounds are capable of enhancing the dissolution process of silk proteins in ionic liquids (ILs) and how silk fibroin nanoparticles (SFNs) can be obtained directly from the silk/ionic liquid solution (SIL) by rapid desolvation in polar organic solvents. The silk fibroin integrity is highly preserved during the dissolution process, as confirmed by sodium dodecyl sulfate‐polyacrylamide gel electrophoresis (SDS‐PAGE) of the SIL. These regenerated SFNs are insoluble in water and other common organic solvents and are indistinguishable from the classical SFNs with respect to their diameter (180 ± 5 nm), Zeta potential (?25 ± 3 mV), high degree of β‐sheet and low cytotoxicity. Large amounts of silk can be turned into biomaterials directly from the SIL solution for use in a wide range of applications, while the ILs can be recovered from the coagulant solution under reduced pressure and reused without loss of their solvent properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41702.     

Kinetic resolution of 1‐phenylethanol integrated with separation of substrates and products by a supported ionic liquid membrane

BACKGROUND: In the present study, the kinetic resolution of rac‐1‐phenylethanol by transesterification with several vinyl esters catalysed by a commercial immobilized Candida antarctica lipase B (Novozym 435) was carried out in n‐hexane at different water contents. The subtrates and products involved in the kinetic resolution were separated using a membrane bioreactor containing a supported liquid membrane based on the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate [bmim⁺][BF₄^?]. RESULTS: Variables affecting the kinetic resolution performance of the enzyme were studied. First, the influence of water content of the medium on the synthetic activity, selectivity and enantioselectivity of the enzyme was analysed in order to establish the optimal amount of water. The use of vinyl esters of different alkyl chain length (vinyl propionate, vinyl butyrate and vinyl laurate) as acyl donors to kinetic resolution was studied. Finally, the integrated reaction/separation process for the resolution of rac‐1‐phenylethanol was carried out in the optimal conditions found. CONCLUSION: These investigations demonstrate that the coupling of lipase enantioselectivity with the selective separation of supported liquid membranes based on ionic liquids provides a promising basis for practical production of enantiomerically pure or enriched compounds. Copyright © 2008 Society of Chemical Industry     

Stabilization of native penicillin G acylase by ionic liquids

Five different ionic liquids, based on dialkylimidazolium cations associated with perfluorinated and bis{(trifluoromethyl)sulfonyl}imide anions, were used to investigate the scope and limitations of these new solvents as media for penicillin G acylase‐catalyzed reactions. Deactivation of the native enzyme in ionic liquids (ILs) and in organic solvents (toluene, dichloromethane and 2‐propanol) at low water content and 40 °C was investigated using the hydrolysis of penicillin G as activity test. Native penicillin G acylase shows greater stability in IL media than in organic solvents. For example, a half‐life time of 23 h was obtained in 1‐ethyl‐3‐methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [emim⁺][Tf₂N^?], which was about 2000‐fold higher than that in 2‐propanol. An enhancement of the PGA stability was observed by the presence of substrate in ionic liquids based on tetrafluoroborate and hexafluorophosphate anions, achieving the highest increase of the half‐life time in 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim⁺][PF₆^?]), which was about 9‐fold higher than the half‐life time in the absence of substrate. Copyright © 2007 Society of Chemical Industry     

Molecular beam epitaxy of c-plane wurtzite GaN on nitridized a-plane β-Ga2O3

Epitaxial growth of GaN on β-Ga₂O₃ single crystal substrates by the molecular beam epitaxy technique is demonstrated for the first time. Standard and in-plane X-ray diffraction evidence the growth of c-plane wurtzite GaN on a-plane β-Ga₂O₃, the epitaxial relationship being 0 1 0_Ga2O3 1 1 2¯ 0_GaN and 0 0 1_Ga2O31¯ 1 0 0_GaN. Epitaxial growth without any buffer layer is achieved after an effective surface nitridation under NH₃ gas.     

Understanding the influence of the ionic liquid composition and the surrounding phase nature on the stability of supported ionic liquid membranes

The industrial application of supported liquid membranes (SLMs) is still limited due to concerns about their stability. In a previous work, the selective separation of the substrates and products of a transesterification reaction was successfully carried out using Nylon membranes impregnated with ionic liquids (ILs). This article analyses the effect of both the IL composition and the nature of the surrounding phase on the stability of these SLMs to design highly stable supported ionic liquid systems. For this purpose, the stability of SLMs based on several ILs after immersion for a week in different feed/receiving phases was characterized using scanning electron microscopy combined with energy dispersive X‐ray (SEM‐EDX). The differential migration of the ILs observed from the membrane toward the surrounding phases was found to be correlated with the solubility of the ILs in the contacting phases. It was observed that SLM stability increased as the polarity of the solvent used as receiving phase decreased and as the hydrophilic character of the ILs used as liquid phase increased. Furthermore, the polymeric support was found to have a strongly stabilizing effect because losses of IL after immersion in a given surrounding phase were much lower than that derived from the solubility of the IL in this phase. © 2011 American Institute of Chemical Engineers AIChE J, 2012