Mc Maaike Kroon

Low-Transition-Temperature Mixtures (LTTMs) : a new generation of designer solvents

A new generation of designer solvents emerged in the last decade as promising green media for multiple applications, including separation processes: the low-transition-temperature mixtures (LTTMs). They can be prepared by mixing natural high-melting-point starting materials, which form a liquid by hydrogen-bond interactions. Among them, deep-eutectic solvents (DESs) were presented as promising alternatives to conventional ionic liquids (ILs). Some limitations of ILs are overcome by LTTMs, which are cheap and easy to prepare from natural and readily available starting materials, biodegradable, and renewable.

New natural and renewable low transition temperature mixtures (LTTMs): screening as solvents for lignocellulosic biomass processing

New natural and biorenewable solvents are prepared in this work consisting of high melting temperature starting materials that form low transition temperature mixtures (LTTMs). The physicochemical behaviour of these new solvents can be tailored by a judicious selection of the constituents’ nature and ratio. Their suitability as solvents for lignocellulosic biomass processing is evaluated.

Hydrophobic deep eutectic solvents as water-immiscible extractants

Hydrophobic deep eutectic solvents (DESs) are presented for the first time. They consist of decanoic acid and various quaternary ammonium salts. The effect of the alkyl chains on the hydrophobicity and the equilibrium of the two-phase DES–water system were investigated. These new DESs were successfully evaluated for the recovery of volatile fatty acids from diluted aqueous solutions.

Tetraalkylammonium oleate and linoleate based ionic liquids: promising extractants for metal salts

In this paper new extractants, that have the potential to be sustainably regenerated, are proposed for metal removal from aqueous phases. These extractants are a novel class of ionic liquids (ILs) with unsaturated fatty acids as anions (oleate and linoleate). The advantages of using these ILs are their simple synthesis, their sustainability (fatty acids anions are renewable), their biocompatibility and their non-toxicity. This makes these ILs “simpler and greener” compared to other solvents used for metal extraction. The newly synthesized ILs were evaluated for extraction of Li, Na, K, Mn(II), Fe(II), and Zn(II) chlorides from aqueous solutions. No or negligible extraction efficiencies were observed for the alkali metal salts, but excellent extraction (>99%) efficiencies were obtained for the period IV transition metal salts.

Enhanced CO2 Capture in Binary Mixtures of 1-Alkyl-3-methylimidazolium Tricyanomethanide Ionic Liquids with Water

Absorption of carbon dioxide and water in 1-butyl-3-methylimidazoliun tricyanomethanide ([C4C1im][TCM]) and 1-octyl-3-methylimidazolium tricyanomethanide ([C8C1im][TCM]) ionic liquids (ILs) was systematically investigated for the first time as a function of the H2O content by means of a gravimetric system together with in-situ Raman spectroscopy, excess molar volume (V(E)), and viscosity deviation measurements. Although CO2 absorption was marginally affected by water at low H2O molar fractions for both ILs, an increase of the H2O content resulted in a marked enhancement of both the CO2 solubility (ca. 4-fold) and diffusivity (ca. 10-fold) in the binary [C(n)C1im][TCM]/H2O systems, in contrast to the weak and/or detrimental influence of water in most physically and chemically CO2-absorbing ILs. In-situ Raman spectroscopy on the IL/CO2 systems verified that CO2 is physically absorbed in the dry ILs with no significant effect on their structural organization. A pronounced variation of distinct tricyanomethanide Raman modes was disclosed in the [C(n)C1im][TCM]/H2O mixtures, attesting to the gradual disruption of the anion-cation coupling by the hydrogen-bonded water molecules to the [TCM](-) anions, in accordance with the positive excess molar volumes and negative viscosity deviations for the binary systems. Most importantly, CO2 absorption in the ILs/H2O mixtures at high water concentrations revealed that the [TCM](-) Raman modes tend to restore their original state for the heavily hydrated ILs, in qualitative agreement with the intriguing nonmonotonous transients of CO2 absorption kinetics unveiled by the gravimetric measurements for the hybrid solvents. A molecular exchange mechanism between CO2 in the gas phase and H2O in the liquid phase was thereby proposed to explain the enhanced CO2 absorption in the hybrid [C(n)C1im][TCM]//H2O solvents based on the subtle competition between the TCM-H2O and TCM-CO2 interactions, which renders these ILs very promising for CO2 separation applications.

Low Transition Temperature Mixtures as Innovative and Sustainable CO2 Capture Solvents

The potential of three newly discovered low transition temperature mixtures (LTTMs) is explored as sustainable substituents for the traditional carbon dioxide (CO2) absorbents. LTTMs are mixtures of two solid compounds, a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA), which form liquids upon mixing with melting points far below those of the individual compounds. In this work the HBD is lactic acid and the HBAs are tetramethylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium chloride. These compounds were found to form LTTMs for the first time at molar ratios of HBD:HBA = 2:1. First, the LTTMs were characterized by determining the thermal operating window (e.g., decomposition temperature and glass transition temperature) and the physical properties (e.g., density and viscosity). Thereafter, the phase behavior of CO2 with the LTTMs has been measured using a gravimetric magnetic suspension balance operating in the static mode at 308 and 318 K and pressures up to 2 MPa. The CO2 solubility increased with increasing chain length, increasing pressure, and decreasing temperature. The Peng-Robinson equation of state was applied to correlate the phase equilibria. From the solubility data, thermodynamic parameters were determined (e.g., Henrys law coefficient and enthalpy of absorption). The heat of absorption was found to be similar to that in conventional physical solvents (-11.21 to -14.87 kJ·mol(-1)). Furthermore, the kinetics in terms of the diffusion coefficient of CO2 in all LTTMs were determined (10(-11)-10(-10) m(2)·s(-1)). Even though the CO2 solubilities in the studied LTTMs were found to be slightly lower than those in thoroughly studied conventional physical solvents, LTTMs are a promising new class of absorbents due to their low cost, their environmentally friendly character, and their easy tunability, allowing further optimization for carbon capture.

PC-SAFT Modeling of CO2 Solubilities in Deep Eutectic Solvents

Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT), a physically based model that accounts for different molecular interactions explicitly, was applied to describe for the first time the phase behavior of deep eutectic solvents (DESs) with CO2 at temperatures from 298.15 to 318.15 K and pressures up to 2 MPa. DESs are mixtures of two solid compounds, a hydrogen bond donor (HBD) and a hydrogen bond acceptor (HBA), which form liquids upon mixing with melting points far below that of the individual compounds. In this work, the HBD is lactic acid and the HBAs are tetramethylammonium chloride, tetraethylammonium chloride, and tetrabutylammonium chloride. Two different modeling strategies were considered for the PC-SAFT modeling. In the first strategy, the so-called pseudo-pure component approach, a DES was considered as a pseudo-pure compound, and its pure-component parameters were obtained by fitting to pure DES density data. In the second strategy, the so-called individual-component approach, a DES was considered to consist of two individual components (HBA and HBD), and the pure-component parameters of the HBA and HBD were obtained by fitting to the density of aqueous solutions containing only the individual compounds of the DES. In order to model vapor-liquid equilibria (VLE) of DES + CO2 systems, binary interaction parameters were adjusted to experimental data from the literature and to new data measured in this work. It was concluded that the individual-component strategy allows quantitative prediction of the phase behavior of DES + CO2 systems containing those HBD:HBA molar ratios that were not used for k(ij) fitting. In contrast, applying the pseudo-pure component strategy required DES-composition specific k(ij) parameters.

Comparison of a low transition temperature mixture (LTTM) formed by lactic acid and choline chloride with choline lactate ionic liquid and the choline chloride salt: physical properties and vapour–liquid equilibria of mixtures containing water and ethanol

A new group of nature-based solvents, i.e. low transition temperature mixtures (LTTMs), are evaluated in this work as entrainers for the separation of azeotropic mixtures. The effect of choline-based LTTMs on the vapour pressure of ethanol and water is compared to the effect of the corresponding lactate-based choline salt and a chloride-based choline salt. The changes with temperature and composition of the physical properties (density and viscosity) of the binary mixtures (entrainer + water–ethanol) are studied and compared. Also, the vapour–liquid equilibrium (VLE) data for binary mixtures of water–ethanol with the studied entrainers are reported. The phase diagrams of the ternary systems composed of water + ethanol + entrainer are shown and the experimental data are correlated by using the e-NRTL model.

Removal of alkali and transition metal ions from water with hydrophobic deep eutectic solvents

Hydrophobic deep eutectic solvents were used for the first time for the removal of metal ions from non-buffered water. It was shown that the extraction occurs via an ion exchange mechanism in which all transition metal ions could be extracted with high distribution coefficients, even for high Co2+ concentrations and low DES/water mass ratios. Maximum extraction efficiency could be reached within 5 s and regeneration was possible.

Correlation between Quantumchemically Calculated LUMO Energies and the Electrochemical Window of Ionic Liquids with Reduction-Resistant Anions

Performing runtime evaluation together with design time exploration enables a system to be more efficient in terms of various design constraints, such as performance, chip area, and power consumption. rSesame is a generic modeling and simulation framework, which can explore and evaluate reconfigurable systems at both design time and runtime. In this paper, we use the rSesame framework to perform a thorough evaluation (at design time and at runtime) of various task mapping heuristics from the state of the art. An extended Motion-JPEG (MJPEG) application is mapped, using the different heuristics, on a reconfigurable architecture, where different Field Programmable Gate Array (FPGA) resources and various nonfunctional design parameters, such as the execution time, the number of reconfigurations, the area usage, reusability efficiency, and other parameters, are taken into consideration. The experimental results suggest that such an extensive evaluation can provide a useful insight both into the characteristics of the reconfigurable architecture and on the efficiency of the task mapping.