Tunable Solvent Research Articles

Evaluation of Alkylimidazoles as Physical Solvents for CO2/CH4 Separation

1-n-Alkylimidazoles are a class of tunable solvents with low volatility and low viscosities. Although imidazoles have been known for some time in the pharmaceutical industry, and as convenient precursors for synthesizing imidazolium-based ionic liquids (ILs), only recently have they been given consideration in some of the same solvent-based separations applications that ILs have been studied for, such as post-combustion CO2 capture and natural gas treating. “Sweetening”, the removal of CO2, H2S, and other “acid” gases from natural gas (CH4), is an existing industrial application where low volatility, low viscosity physical solvents are already applied successfully and economically at large scale. Physical solvents are also used for syngas cleanup and in the emerging application of pre-combustion CO2 capture. Given the similarities in physical properties between 1-n-alkylimidazoles, and physical solvents currently used in industrial gas treating, the 1-n-alkylimidazole class of solvents warrants further investigation. Solubilities of CO2 and CH4 in a series of 1-n-alkylimidazoles were measured under conditions relevant to the use of physical solvents for natural gas treating: ∼5 atm partial pressure of CO2 and temperatures of 30–75 °C. Solubilities of CO2 and CH4 were found to be strongly dependent on temperature, with the solubility of each gas in all solvents diminishing with increasing temperature, although CO2 exhibited a stronger temperature dependence than CH4. Ideal CO2/CH4 solubility selectivities were also more favorable at lower temperatures in 1-n-alkylimidazole solvents with shorter chain lengths. CO2 solubility decreased with increasing chain length, while CH4 solubility exhibited a maximum in 1-hexylimidazole. The solubility trends observed with temperature and chain length can be explained through calculation of solution enthalpies and solvent fractional free volume as approximated from van der Waals volumes as calculated via atomic contributions. Of the solvents examined, 1-methylimidazole displays the most favorable CO2 solubility and CO2/CH4 selectivity, and has the lowest viscosity. A comparison of 1-methylimidazole to commercially used solvents reveals similar physical properties and the potential for use in industrial gas processing. Imidazolium-based ILs are also compared, although they appear less favorable for use within established process schemes given their higher viscosities and reduced capacity for CO2.

Novel Solvents for Sustainable Production of Specialty Chemicals

We discuss novel solvents that improve the sustainability of various chemical reactions and processes. These alternative solvents include organic-aqueous tunable solvents; near-critical water; switchable piperylene sulfone, a volatile dimethylsulfoxide substitute; and reversible ionic liquids. These solvents are advantageous to a wide variety of reactions because they reduce waste and energy demand by coupling homogeneous reactions with heterogeneous separations, acting as in situ acid or base catalysts, and providing simple and efficient postreaction separations.

ChemInform Abstract: Liquid‐Crystal Nanoscience: An Emerging Avenue of Soft Self‐Assembly

AbstractReview: 89 refs.

Exploiting Phase Behavior for Coupling Homogeneous Reactions with Heterogeneous Separations in Sustainable Production of Pharmaceuticals

John Prausnitz was never content to measure new data solely because the data were new. He always had an application in mind—a separation or even a process that required the data for implementation. We present here an advance in using designed changes in phase equilibria to enable the facile recovery and recycle of homogeneous catalysts. We show a new application of organic-aqueous tunable solvents (OATS) to run homogeneous reactions (fast rates and high selectivities) followed by facile and efficient heterogeneous separations and the recycle of the homogeneous catalysts. This is done by using CO2 to manipulate the phase behavior of monophasic organic−water mixtures to form heterogeneous organic-rich and aqueous-rich phases. The example shown is the hydroformylation of hydrophobic p-methylstyrene catalyzed by rhodium catalyst to which is attached a hydrophilic phosphorus ligand. The OATS method increases the conversion rate of styrene to the aldehyde products by an order of magnitude compared to heterogeneously reported reactions. Also, the selectivity toward the branched aldehyde (the desired product) increases by 30 %. The hydrophobic product partitions into the organic-rich phase with more than 99 % removal efficiency, and the hydrophilic catalyst is retained in the aqueous-rich phase with 99.9 % efficiency. In addition, we recycle the catalyst for five consecutive reactions without significant loss of catalytic activity.

Liquid-crystal nanoscience: an emerging avenue of soft self-assembly

Liquid crystals are finding increasing applications in a wide variety of fields including liquid-crystal display technology, materials science, bioscience, etc., apart from acting as prototype self-organizable supramolecular soft materials and tunable solvents. Recently, keeping in pace with topical science, liquid crystals have entered into the fascinating domains of nanoscience and nanotechnology. This tutorial review describes the recent and significant developments in liquid-crystal nanoscience embracing contemporary nanomaterials such as nanoparticles, nanorods, nanotubes, nanoplatelets, etc. The dispersion of zero-, one- and two-dimensional nanomaterials in liquid crystals for the enhancement of properties, liquid-crystalline phase behavior of nanomaterials themselves, self-assembly and alignment of nanomaterials in liquid-crystalline media, and the synthesis of nanomaterials by using liquid crystals as 'templates' or 'precursors' have been highlighted and discussed. It is almost certain that the 'fourth state of matter' will play more prevalent roles in nanoscience and nanotechnology in the near future. Moreover, liquid-crystal nanoscience reflects itself as a beautiful demonstration of the contemporary theme "crossing the borders: science without boundaries".

Combining the Benefits of Homogeneous and Heterogeneous Catalysis with Tunable Solvents and Nearcritical Water

The greatest advantage of heterogeneous catalysis is the ease of separation, while the disadvantages are often limited activity and selectivity. We report solvents that use tunable phase behavior to achieve homogeneous catalysis with ease of separation. Tunable solvents are homogeneous mixtures of water or polyethylene glycol with organics such as acetonitrile, dioxane, and THF that can be used for homogeneously catalyzed reactions. Modest pressures of a soluble gas, generally CO2, achieve facile post-reaction heterogeneous separation of products from the catalyst. Examples shown here are rhodium-catalyzed hydroformylation of 1-octene and p-methylstyrene and palladium catalyzed C-O coupling to produce o-tolyl-3,5-xylyl ether and 3,5-di-tert-butylphenol. Both were successfully carried out in homogeneous tunable solvents followed by separation efficiencies of up to 99% with CO2 pressures of 3 MPa. Further examples in tunable solvents are enzyme catalyzed reactions such as kinetic resolution of rac-1-phenylethyl acetate and hydrolysis of 2-phenylethyl acetate (2PEA) to 2-phenylethanol (2PE). Another tunable solvent is nearcritical water (NCW), whose unique properties offer advantages for developing sustainable alternatives to traditional processes. Some examples discussed are Friedel-Crafts alkylation and acylation, hydrolysis of benzoate esters, and water-catalyzed deprotection of N-Boc-protected amine compounds.

Solubility, Solubility Modeling, and Precipitation of Naproxen from Subcritical Water Solutions

In this paper, the solubility of naproxen in subcritical water (SBCW) between 130 and 170 °C is measured. The solubility of naproxen in SBCW was correlated to temperature using a Modified Universal Functional Activity Coefficient (M-UNIFAC) model. Errors in the model were minimized by optimizing the water−carboxylic acid interaction parameter, as other side groups were already optimized. The micronization of naproxen via processes that used the tunable solvent power of SBCW was conducted. Two precipitation techniques were developed. In the first technique, the temperature of a SBCW solution containing naproxen was rapidly quenched by injection into cold water solutions. The quenching media were either pure water or 1% w/v solution of lactose in water. Variations in SBCW−naproxen solution injection temperature and supersaturation ratios in pure water were examined. Product morphology was robust toward changes in operating conditions and consisted of flaky crystals with a particle size distribution ranging ...

Organic Aqueous Tunable Solvents (OATS): A Vehicle for Coupling Reactions and Separations

In laboratory-based chemical synthesis, the choice of the solvent and the means of product purification are rarely determined by cost or environmental impact considerations. When a reaction is scaled up for industrial applications, however, these choices are critical: the separation of product from the solvent, starting materials, and byproduct usually constitutes 60-80% of the overall cost of a process. In response, researchers have developed solvents and solvent-handling methods to optimize both the reaction and the subsequent separation steps on the manufacturing scale. These include "switchable" solvents, which are designed so that their physical properties can be changed abruptly, as well as "tunable" solvents, wherein the solvent's properties change continuously through the application of an external stimulus. In this Account, we describe the organic aqueous tunable solvent (OATS) system, examining two instructive and successful areas of application of OATS as well as its clear potential for further refinement. OATS systems address the limitations of biphasic processes by optimizing reactions and separations simultaneously. The reaction is performed homogeneously in a miscible aqueous-organic solvent mixture, such as water-tetrahydrofuran (THF). The efficient product separation is conducted heterogeneously by the simple addition of modest pressures of CO(2) (50-60 bar) to the system. Under these conditions, the water-THF phase splits into two relatively immiscible phases: the organic THF phase contains the hydrophobic product, and the aqueous phase contains the hydrophilic catalyst. We take advantage of the unique properties of OATS to develop environmentally benign and cost-competitive processes relevant in industrial applications. Specifically, we describe the use of OATS for optimizing the reaction, separation, design, and recycling of (i) Rh-catalyzed hydroformylation of olefins such as 1-octene and (ii) enzyme-catalyzed hydrolysis of 2-phenylacetate. We discuss the advantages of these OATS systems over more traditional processes. We also consider future directions that can be taken with these proven systems as well as related innovations that have recently been reported, including the use of poly(ethylene glycol) (PEG) as a tunable adjunct in the solvent and the substitution of propane for CO(2) as the external stimulus. OATS systems in fact represent the ultimate goal for a sustainable process, because in an idealized setup there is only reactant coming in and product going out; in principle, there is no waste stream.

Continuous-flow homogeneous catalysis using the temperature-controlled solvent properties of supercritical carbon dioxide

A fully integrated continuous process for homogeneous catalysed reactions in scCO(2) has been developed exploiting the tunable solvent properties of scCO(2). A heated condenser situated above the reaction zone leads to a phase split under isobaric conditions resulting in efficient catalyst retention and recirculation. Continuous isomerisation of allylic alcohols was carried out for over 200 hours time-on-stream demonstrating the viability of this approach.

Ionic liquids in surface electrochemistry

Ionic liquids (IL) are widely used in electrochemistry due to their excellent properties such as good ionic conductivity, wide electrochemical potential window, high viscosity, high thermal stability, wide liquid range and tunable solvent properties. In electrochemistry, the performance of an electrochemical system is dependent on the properties of the interface at the IL/electrode. This review presents the surface electrochemistry in ILs, and the interfacial structures of IL/electrode and heterogeneous electron-transfer kinetics are detailed. Finally, the updated researches on the electrochemical applications of ILs such as electrode deposition, electrosynthesis, electrocatalysis, electrochemical biosensing, electrochemical capacitor and lithium batteries are demonstrated.

Combining Homogeneous Catalysis with Heterogeneous Separation using Tunable Solvent Systems

Tunable solvent systems couple homogeneous catalytic reactions to heterogeneous separations, thereby combining multiple unit operations into a single step and subsequently reducing waste generation and improving process economics. In addition, tunable solvents can require less energy than traditional separations, such as distillation. We extend the impact of such solvents by reporting on the application of two previously described carbon dioxide tunable solvent systems: polyethylene glycol (PEG)/organic tunable solvents (POTS) and organic/aqueous tunable solvents (OATS). In particular, we studied: (1) the palladium catalyzed carbon-oxygen coupling of 1-bromo-3,5-dimethylbenzene and o-cresol to potassium hydroxide to produce o-tolyl-3,5-xylyl ether and 1-bromo-3,5-di-tert-butylbenzene to potassium hydroxide to produce 3,5-di-tert-butylphenol in PEG400/1,4-dioxane/water and (2) the rhodium-catalyzed hydroformylation of p-methylstyrene in water/acetonitrile to form 2-(p-tolyl) propanal. In addition, we introduce a novel tunable solvent system based on a modified OATS where propane replaces carbon dioxide. This represents the first use of propane in a tunable solvent system.

ChemInform Abstract: Ethyl Lactate as a Tunable Solvent for the Synthesis of Aryl Aldimines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Guide to CO2 Separations in Imidazolium-Based Room-Temperature Ionic Liquids

Room-temperature ionic liquids (RTILs) are nonvolatile, tunable solvents that have generated significant interest across a wide variety of engineering applications. The use of RTILs as media for CO2 separations appears especially promising, with imidazolium-based salts at the center of this research effort. The solubilities of gases, particularly CO2, N2, and CH4, have been studied in a number of RTILs. Process temperature and the chemical structures of the cation and anion have significant impacts on gas solubility and gas pair selectivity. Models based on regular solution theory and group contributions are useful to predict and explain CO2 solubility and selectivity in imidazolium-based RTILs. In addition to their role as a physical solvent, RTILs might also be used in supported ionic liquid membranes (SILMs) as a highly permeable and selective transport medium. Performance data for SILMs indicates that they exhibit large permeabilities as well as CO2/N2 selectivities that outperform many polymer membra...

Ethyl lactate as a tunable solvent for the synthesis of aryl aldimines

Ethyl L-lactate can be tuned with a cosolvent to create polarity conditions ideal for synthesizing aryl aldimines that crystallize directly out of solution within minutes under ambient conditions in excellent yields and requiring no further purification.

Hydroformylation Catalyst Recycle with Gas-Expanded Liquids

Tunable solvents such as gas-expanded liquids offer unique opportunities as benign and economic reaction media. We have improved the turnover frequency of a water-soluble catalyst system by a factor of 85 for the hydroformylation of 1-octene by using a tunable solvent system, which also increases substrate solubility. In our approach, the reaction is run homogeneously in a miscible water−organic solution, and after reaction, CO2 is used as a “miscibility switch” for efficient product and catalyst recovery. Two water-soluble ligands, TPPTS (tris(3-sulfophenyl)phosphine) and TPPMS ((3-sulfophenyl)diphenylphosphine), were compared to triphenylphosphine for hydroformylation activity of their rhodium complexes. The catalyst was recycled three times with no loss of activity.

Thermodynamic Analysis of Nanoparticle Size Selective Fractionation Using Gas-Expanded Liquids

A thermodynamic model was developed for the size-selective fractionation of ligand-stabilized nanoparticles by a CO2 gas-expanded liquid precipitation process. The tunable solvent strength of gas-expanded liquids, via CO2 pressurization, results in an effective method to fractionate nanoparticles, based on the size-dependent dispersibility of the particles. Specifically, the thermodynamic model is used to estimate the size of dodecanethiol-capped Ag nanoparticles that can be dispersed at a given CO2 pressure by equating the total interparticle interaction energy to the Boltzmann threshold stabilization energy (−3/2kBT). The ligand−solvent interaction is found to have the greatest impact on the total interaction energy. This model illustrates that the entire length of the ligand is not accessible to the solvent, and three phenomenological model variations were developed to vary the ligand−solvent interaction.

Biocompatible, Lactide-Based Surfactants for the CO2−Water Interface: High-Pressure Contact Angle Goniometry, Tensiometry, and Emulsion Formation

The unique properties of compressed CO2, including its low cost, nontoxicity, easily tunable solvent strength, and favorable transport properties, make it an environmentally attractive alternative to volatile organic solvents. Suitable surface-active species can be utilized to realize the full potential of clean, CO2-based technologies, by helping to overcome the low solubility typically associated with many solutes of interest in CO2. In this work we synthesize and investigate the interfacial activity of a series of nonionic amphiphiles with a biocompatible and biodegradable CO2-phile at both the CO2-water (C|W) and CO2-water-solid (C|W|S) interfaces. We developed a high-pressure pendant drop tensiometer and contact angle goniometer that allows us to measure both tension and contact angle in tandem. The tension of the C|W interface was measured in the presence of the lactide (LA)-based surface active agents with varying molecular weight and hydrophilic-to-CO2-philic ratios. Emulsion studies with an optimum balanced surfactant were performed. The contact angle of water droplets against a silane-modified (hydrophobic) substrate under CO2 atmosphere was also measured in presence of a selected LA-based amphiphile. The results demonstrate that the nonionic copolymers with the biodegradable and biocompatible LA-based group can significantly reduce the tension of the C|W interface. The LA-based surface active species are also capable of forming stable emulsions of water and CO2 and reducing the angle of the three-phase C|W|S contact line.

Finely Controlled Size-Selective Precipitation and Separation of CdSe/ZnS Semiconductor Nanocrystals Using CO2-Gas-Expanded Liquids

A technique was developed to size-selectively separate polydisperse dispersions of CdSe/ZnS nanocrystals into distinct color fractions using only the tunable solvent properties of CO2-expanded hexane. This size-selective precipitation of semiconductor nanoparticles is achieved by finely tuning the solvent strength of the CO2/hexane medium by simply adjusting the applied CO2 pressure. These subtle changes affect the balance between osmotic repulsive and van der Waals attractive forces, thereby allowing fractionation of the nanocrystals into multiple narrow size populations.

Tunable solvents for fine chemicals from the biorefinery

Making biorefineries economically and environmentally sustainable is the biggest barrier to the mass commercialization of biofuels in this country. One way to add economic value to the biofuel process is to isolate and extract fine chemicals from waste biomass such as lignin, extractives, and unreacted cellulose and hemicellulose. In this paper we demonstrate a technique for extracting high-value added chemicals such as vanillin, syringaldehyde, and syringol from lignin using a novel CO2-expanded organic solvent (gas-expanded liquid). This method incorporates many principles of green chemistry while offering several economical advantages to the biorefinery: low operating costs, easy recycling of organic solvents, use of a renewable feedstock, and a way to produce chemicals without wasteful synthesis. Furthermore, this technique demonstrated the ability to produce high-value chemicals ($5–25 lb−1) from a waste source that is presently being burned for a fuel value of 2–3 cents lb−1. We believe the process presented in this paper will spark interest in developing other sustainable techniques to extract fine chemicals from biorefinery waste.

Coupling chiral homogeneous biocatalytic reactions with benign heterogeneous separation

We describe a method for sustainable biocatalysis in an organic aqueous tunable solvent (OATS) system in which a hydrophobic substrate is transformed with a homogeneous enzymatic catalyst in a single liquid phase. Subsequent CO2 addition produces a biphasic mixture where the hydrophobic product partitions preferentially into the organic rich phase for separation while the hydrophilic enzyme catalyst partitions into the aqueous rich phase, where it is recyclable. Greater than 99% enantiomeric excess (ee) is shown for catalyzed hydrolysis of rac-1-phenylethyl acetate with Candida antarctica lipase B (CAL B) both before and after CO2-induced separation. Additionally, processing parameters in OATS systems are discussed. This system combines homogeneous enzymatic reactions with a built-in heterogeneous separation for enantiomerically pure products.