Design of Gas Separation Processes Using Type II Porous Liquids as Physical Solvents
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Solvation Thermodynamics of Solutes in Water and Ionic Liquids Using the Multiscale Solvation-Layer Interface Condition Continuum Model
We report molecular assembly processes are generally driven by thermodynamic properties in solutions. Atomistic modeling can be very helpful in designing and understanding complex systems, except that bulk solvent is very inefficient to treat explicitly as discrete molecules. The SLIC/CDC multiscale model combines continuum solvent electrostatics based on the solvent layer interface condition (SLIC) with statistical thermodynamic models for hydrogen bonding and nonpolar modes: cavity formation, dispersion interactions, combinatorial mixing (CDC). The SLIC/CDC model predicts Gibbs energies of solvation for a database of 500 solutes in water with average accuracy better than 1 kcal/mol both for experimental measurements and for explicit-solvent molecular dynamics simulations. The separate SLIC/CDC energy mode values agree quantitatively with those computed from explicit-solvent molecular dynamics. The SLIC/SASA multiscale model combines the SLIC continuum electrostatic model with the solvent accessible surface area (SASA) nonpolar energy mode. The SLIC/SASA model predicts Gibbs energies of solvation with better than 1.4 kcal/mol average accuracy in aqueous systems and better than 1.6 kcal/mol average accuracy in ionic liquids. Both models predict solvation entropies, and are the first implicit-solvation models capable of predicting solvation heat capacities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Investigating the Variation in Solvation Interactions of Choline Chloride-Based Deep Eutectic Solvents Formed Using Different Hydrogen Bond Donors
Choline chloride-based deep eutectic solvents (DESs) have gained widespread recognition as green solvents in catalysis and separation science as their designer properties permit solvation properties to be modulated by the choice of the hydrogen bond donor (HBD) as well as its molar ratio. Despite being one of the most popular classes of DESs, very little is currently understood regarding how their solvation characteristics differ among themselves as well as from other classes of DESs. Previous studies have shown that the catalytic activity, extraction efficiency, and solubilities of natural compounds can be influenced by the type of choline salt and HBD, but no study has systematically related these parameters with its solvation properties. In this study, inverse gas chromatography was employed for the first time to study the individual solvation characteristics of a diverse range of choline chloride and acetate-based DESs composed of amides, diols, organic acids, and carbohydrates. Furthermore, hydrogen bond acidity was found to be a dominant interaction for all DESs, especially those composed of organic acid HBDs. DESs composed of isomers of butane diol and hexane diol as HBDs exhibited higher hydrogen bond basicity and dispersive-type interactions compared to those composed of urea, acetamide, and organic acids with the position of the hydroxyl functional group influencing their solvation interactions. Choline acetate-based DESs exhibited lower dipolarity and stronger hydrogen bond basicity and dispersive-type interactions compared to choline chloride DESs. The solvation models developed in this study were used to interpret and explain DES behavior in previously reported studies involving catalysis, organic synthesis, and extractions demonstrating that the measured solute–solvent interactions can serve to predict the performance of choline chloride-based DESs when used in various applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The Role of the Anion in Imidazolium-Based Ionic Liquids for Fuel and Terpenes Processing
The potentialities of methylimidazolium-based ionic liquids (ILs) as solvents were evaluated for some relevant separation problems—terpene fractionation and fuel processing—studying selectivities, capacities, and solvent performance indices. The activity coefficients at infinite dilution of the solute (1) in the IL (3), γ13∞, of 52 organic solutes were measured by inverse gas chromatography over a temperature range of 333.2–453.2 K. The selected ILs are 1-butyl-3-methylimidazolium hexafluorophosphate, [C4mim][PF6], and the equimolar mixture of [C4mim][PF6] and 1-butyl-3-methylimidazolium chloride, [C4mim]Cl. Generally, low polar solutes follow γ1,C4mimCl∞ > γ1,C4mimPF6+C4mimCl∞ > γ1,C4mimPF6∞ while the opposite behavior is observed for alcohols and water. For citrus essential oil deterpenation, the results suggest that cations with long alkyl chains, such as C12mim+, promote capacity, while selectivity depends on the solute polarity. Promising results were obtained for the separation of several model mixtures relevant to fuel industries using the equimolar mixture of [C4mim][PF6] and [C4mim]Cl. This work demonstrates the importance of tailoring the polarity of the solvents, suggesting the use of ILs with mixed anions as alternative solvents for the removal of aliphatic hydrocarbons and contaminants from fuels.
Zambom, Aline (ORCID:0000000324512716)↗
Separation of a target substance from a fluid or mixture using encapsulated sorbents
Method and apparatus for separating a target substance from a fluid or mixture. Capsules having a coating and stripping solvents encapsulated in the capsules are provided. The coating is permeable to the target substance. The capsules having a coating and stripping solvents encapsulated in the capsules are exposed to the fluid or mixture. The target substance migrates through the coating and is taken up by the stripping solvents. The target substance is separated from the fluid or mixture by driving off the target substance from the capsules.
Aines, Roger D.↗
Condensation-based redox flow battery rebalancing
In a redox flow battery (RFB), the base solvent of the electrolytes tends to migrate across the barrier layer from one electrode toward the other. This can result in a volume and concentration imbalance between the electrolytes that is detrimental to battery efficiency and capacity. Compatible electrolytes can be mixed to rebalance the system, but for incompatible electrolytes mixing is not a viable option. To this end, the RFB herein includes a separator that recovers base solvent from the vapor phase of one of the electrolytes and returns the recovered base solvent to the other electrolyte to thereby reverse the imbalance.
Saraidaridis, James D.↗
Solvent selection for biphasic extraction of 5-hydroxymethylfurfural via multiscale modeling and experiments
We introduce a comprehensive conceptual framework for selecting solvents for reactive extraction in biphasic organic-water systems and demonstrate it for the separation of HMF (5-hydroxylmethylfurfural), a platform chemical produced in the acid-catalyzed dehydration of hexoses. We first perform in silico screening of ~2500 solvents, from the ADFCRS-2018 database using the ADF COSMO-RS implementation, and classification, based on the solvent partition coefficient. We then determine experimentally the partition coefficients for HMF, fructose, and products of HMF rehydration (levulinic acid (LA), and formic acid (FA)), the mutual water-organic solvent solubilities, and the separation factors in >50 select solvents spanning multiple homologous series at room temperature and a typical reaction temperature with in situ sampling. We find that COSMO-RS is excellent for screening purposes (typical error in most cases within a factor of ~2). Increased temperatures lead to significant reduction in partitioning, and room temperature measurements are clearly inadequate for solvent selection. Upon down selecting classes of solvents based on separation performance, we perform experimental thermal stability and reaction compatibility studies of a small set of solvents at relevant reactive-extraction temperatures. We discover that many substituted phenols exhibit an order-of-magnitude increase in partitioning compared to conventional solvents due chiefly to hydrogen bond interactions and show the necessary stability but retain a significant fraction of water and LA, factors that need to be considered in technoeconomic analysis. In contrast, anilines, aldehydes, and acids are good to excellent regarding separation but incompatible with this specific reaction medium. Furthermore, this multifaceted framework can be extended to other biomass-derived products and processes.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Process design for recovering rare-earth elements from mine tailings with low rare-earth concentrations via sequential leaching and solvent extraction
Rare earth elements (REEs) are essential for advanced technologies and yet face significant supply chain risks due to their concentrated global production and limited domestic availability. Addressing this challenge requires efficient processes capable of upgrading low-grade secondary resources such as mine tailings. In this study, we developed a novel separation flowsheet that integrates sequential leaching and 2-stage solvent extraction (SX) processes to recover high-purity heavy REEs (HREEs) and light REEs (LREEs) from a simulated mine-tailing concentrate containing 2.4 wt% total REEs (TREEs; 0.6 wt% LREEs and 1.8 wt% HREEs). Sequential leaching with controlled pH adjustment selectively precipitated REEs while retaining the large amount of impurities in the solution, producing an REE-enriched leachate by following leaching processes with roughly twice the REE concentration and half the impurity concentration compared to that of single-step leaching. The optimized SX flowsheet employed Cyanex 572 to extract HREEs and Fe over LREEs, followed by Fe removal using tributyl phosphate (TBP), while the raffinate stream was processed by SX with di(2-ethylhexyl)phosphoric acid (D2EHPA) to recover LREEs under optimized conditions balancing both extraction efficiency and purity. Although increased extractant availability in the organic phase improved LREE recovery, it also increased co-extraction of Ca, underscoring trade-offs in process optimization. Both HREE- and LREE-rich solutions were subsequently precipitated into solid products via oxalate precipitation, resulting in high-purity REE solids containing ∼92.0 wt% HREEs (∼95.7 wt% TREEs) and ∼92.8 wt% LREEs (∼94.0 wt% TREEs). In conclusion, this proof-of-concept study using simulated mine tailings demonstrates a promising approach for upgrading low-grade REE resources, while highlighting the need for future validation with real materials.
Mine tailings↗
Off-gas capture: a promising strategy for removal and recovery of toxic bioproducts in aerobic fermentation
In many bioprocesses, maximum achievable titers are limited below economically viable levels by toxic accumulation of the primary end-product. To combat end-product inhibition, a variety of in situ product removal technologies have been developed to selectively remove or partition toxic bioproducts, thereby prolonging fermentation and improving overall process efficiency. Use of an in situ organic overlay to partition toxic hydrophobic products is a commonly employed approach, but this technique occupies valuable space in the fermentor, imposes replacement costs for unrecovered solvent, and increases downstream separation due to formation of stable emulsions. In addition, for many volatile hydrophobic products produced under aerobic conditions—including medium-chain alcohols, esters, monoterpenes, and other aviation fuel precursors—a significant fraction of the product is volatilized to the fermentor off-gas and must be recovered separately to maximize product yield. To address these challenges, we explore the viability of leveraging existing aeration energy to fully strip and recover volatile products from the fermentor off-gas. We compare two strategies of in situ product removal—liquid–liquid extraction and direct recovery from fermentation off-gas—for the production and recovery of intermediates used to generate isoprene and DMCO (1,4-dimethylcyclooctane), a high-performance jet fuel. We evaluate product toxicity, solvent toxicity, solvent partitioning, and the impact of aeration and internal overlay configurations on product volatilization rates. We then optimize product recovery from fermentor off-gas via condensation in chilled solvent, achieving 84% capture efficiency. In addition to greatly simplifying downstream processing, relying on aeration for product volatilization in the absence of an internal overlay enables continuous removal of toxic fermentation products up to maximum isoprenol titers of 20.4 g/L, the highest reported to date.
isoprene↗
Genomic characterization of rare earth binding by Shewanella oneidensis
Abstract Rare earth elements (REE) are essential ingredients of sustainable energy technologies, but separation of individual REE is one of the hardest problems in chemistry today. Biosorption, where molecules adsorb to the surface of biological materials, offers a sustainable alternative to environmentally harmful solvent extractions currently used for separation of rare earth elements (REE). The REE-biosorption capability of some microorganisms allows for REE separations that, under specialized conditions, are already competitive with solvent extractions, suggesting that genetic engineering could allow it to leapfrog existing technologies. To identify targets for genomic improvement we screened 3,373 mutants from the whole genome knockout collection of the known REE-biosorbing microorganism Shewanella oneidensis MR-1. We found 130 genes that increased biosorption of the middle REE europium, and 112 that reduced it. We verified biosorption changes from the screen for a mixed solution of three REE (La, Eu, Yb) using Inductively Coupled Plasma Mass Spectrometry (ICP-MS) in solution conditions with a range of ionic strengths and REE concentrations. We identified 18 gene ontologies and 13 gene operons that make up key systems that affect biosorption. We found, among other things, that disruptions of a key regulatory component of the arc system ( hptA ), which regulates cellular response to anoxic environments and polysaccharide biosynthesis related genes ( wbpQ , wbnJ , SO_3183 ) consistently increase biosorption across all our solution conditions. Our largest total biosorption change comes from our SO_4685 , a capsular polysaccharide (CPS) synthesis gene, disruption of which results in an up to 79% increase in biosorption; and nusA, a transcriptional termination/anti-termination protein, disruption of which results in an up to 35% decrease in biosorption. Knockouts of glnA , pyrD , and SO_3183 produce small but significant increases (≈ 1%) in relative biosorption affinity for ytterbium over lanthanum in multiple solution conditions tested, while many other genes we explored have more complex binding affinity changes. Modeling suggests that while these changes to lanthanide biosorption selectivity are small, they could already reduce the length of repeated enrichment process by up to 27%. This broad exploratory study begins to elucidate how genetics affect REE-biosorption by S. oneidensis , suggests new areas of investigation for better mechanistic understanding of the membrane chemistry involved in REE binding, and offer potential targets for improving biosorption and separation of REE by genetic engineering.
Medin, Sean↗
A structural underpinning of the lower critical solution temperature (LCST) behavior behind temperature-switchable liquids
In this work, we use state-of-the-art X-ray scattering and molecular dynamics to analyze amine-water mixtures that show the unusual lower critical solution temperature (LCST) behavior. The goal is to provide direct experimental evidence for the entropy-lowering molecular cluster formation hypothesized as necessary for LCST behavior. Differential wide-angle X-ray scattering and pair distribution analysis and small-angle X-ray scattering measurements were combined with molecular modeling and liquid-liquid equilibrium measurements, revealing direct experimental evidence for the hypothesis. However, the response of the amine phase to accommodating water is even more subtle than the simple hypothesis suggests, with the formation of robust nanoscale reverse micelles. The techniques developed in this paper can be expected to yield insights in the use of temperature-switchable liquids in solvent extraction and other separations, and the stabilization of organelles in living cells that do not have physical membranes but do require compositional gradients to operate.
36 MATERIALS SCIENCE↗
An Explainable Classification Framework for Determining and Understanding the Suitability of Solvent Extraction for Bioproduct Recovery
Lignocellulosic biomass is an abundant feedstock for producing sustainable fuels and chemicals. However, a key challenge in most biomass utilization strategies is the recovery of products from a dilute, typically aqueous, phase. In this respect, liquid–liquid extraction, which relies on a solvent to transfer a product of interest from one liquid phase to another (solvent-rich) phase, is a technology that can reduce the energy requirements for product recovery. To reduce solvent consumption, liquid–liquid extraction needs to be combined with another separation method (e.g., distillation) to recycle the solvent. Despite the research on solvent extraction, there are limited system-wide methods that allow us to determine when extraction is well suited to carry out a specific separation. Accordingly, we present a classification framework to predict whether extraction, coupled with distillation, is feasible and more economical than distillation. Our framework is based on features such as feed composition, liquid–liquid equilibrium constants, relative volatilities, and solvent price, and leads to trained classifiers that show good prediction accuracy. We further study how specific features influence the suitability of extraction. Furthermore, to showcase the applicability of the framework, we use it to analyze the separation of acetic acid from water.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ternary Phase Diagram of Water/Bio-Oil/Organic Solvent for Bio-Oil Fractionation
Separating bio-oil by fractionation with different chemical composition is a critical step to refine these oils and obtain high value products. Cold-water precipitation of pyrolytic lignin from bio-oil is the most common approach used. However, the obtained aqueous phase from this method still contain phenols, is diluted and difficult to use. In this study, the use of liquid-liquid extraction with different solvents (1-butanol, ethyl acetate, 1-octanol, dichloromethane, toluene, and hexane) for the separation of targeted molecules (lignin oligomers, sugars, acetic acid) is explored. Ternary phase diagrams for the organic solvent/water/bio-oil are reported. The partition coefficient of compounds of interest (both light and heavy fraction) is reported for the liquid-liquid equilibrium zone. When using butanol as solvent, the highest separation factor of total phenols over total sugars was observed. Furthermore, our results provide information to design L-L separation units with the capacity to selectively recover targeted molecules from pyrolysis oils.
09 BIOMASS FUELS↗
Development of a Lower Cost, High Volume, Commercially Available, Precursor for Lower Cost Carbon Fiber for Automotive and Wind Blade Applications
Essentially all carbon fibers used in structural applications are presently manufactured from solution spun polyacrylonitrile (PAN) precursor. Solution spinning is accomplished at relatively low temperatures using very large amounts of environmentally unfriendly solvents that impart major impact to line speed and costs involved with handling and reclaiming the solvents and associated “waste streams” required in spinning and extracting those solvents. Dralon and others have demonstrated the dry spinning of PAN in the production of some acrylic fibers for textile applications, but to this point it has not been demonstrated in the production of carbon fibers. In dry spinning, the PAN polymer is also dissolved into similar solvents, although typically less solvent is utilized to maintain a somewhat higher solids content of 20-50%. The use of lower overall solvent quantities and elimination of the need for solvent/water separation simplifies and reduces the cost of solvent recovery operations. Other portions of the precursor production and carbon fiber manufacturing processes are quite similar. The work described in this report demonstrated that dry spun acrylic fiber can be an attractive candidate for carbon fiber precursor of potential interest to applications looking to capture the specific stiffness (stiffness per unit mass) and specific strength (strength per unit mass) of carbon fiber when produced at a discount relative to commercial carbon fibers in the market today. Dralon has determined that the dry spinning process utilized for producing fibers used as precursors in this project requires 27% less energy versus producing comparable fibers via the industry standard wet spinning process. Identification of carbon fiber manufacturers, as well as applications development and targeted marketing, will be required to achieve significant in-roads into mission areas of interest to DOE, such as automotive applications and wind turbine blades. In support of that activity, initial data produced in this project indicate the innovative approach as described in this report can meet at least the baseline property requirements identified for these applications.
36 MATERIALS SCIENCE↗
Interinstitutional Study of the New EURO-GANEX Process Resistance by Gamma Irradiation Test Loops
As part of the homogeneous actinides recycling strategy, the EURO-GANEX process is one of the most promising options to achieve the goal of minor actinides recovery. However, EURO-GANEX also has various drawbacks that are being addressed. Improvements made to EURO-GANEX system have resulted in the emergence of the so-called New EURO-GANEX process, where the composition of the solvent has been modified by replacing TODGA and DMDOHEMA with cis-mTDDGA in the organic phase and SO3-Ph-BTP with PyTri-Diol in the aqueous phase in order to resolve important issues. The objective of this work is twofold: evaluate the gamma radiolysis resistance of the new EURO-GANEX process by dynamic irradiation conditions simulating the three main steps of the process and validate the design of CIEMAT Náyade, CEA Marcel and INL irradiation loop devices since each of them mimics different aspects of the real process. Náyade and the INL loops could irradiate together the organic and aqueous phases, whereas in the CEA loop, the irradiated solvent is recycled continuously inside a platform with several stages of mixer-settlers containing aqueous flows simulating the three main steps of the process. The extraction performances and changes in the composition of the solvent have been analysed during the irradiation experiment by different techniques: gamma spectrometry and ICP-MS/OES for cations or tracers extraction, and HPLC-MS to quantify the degradation and evaluate the degradation compounds. Additionally, in spite of some differences between the three-irradiation facilities, this inter-institutional study shows that they are three comparative tools, which provide results on the stability towards radiolysis of a liquid-liquid extraction system. Favourable extraction results for the different steps are obtained according to the static irradiation studies found in literature. However, the degradation of cis-mTDDGA is appreciable leading to degradation compounds, some of which form precipitates and produce important changes in viscosity, important aspects that must be addressed prior to the successful industrial application of the new EURO-GANEX process.
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
Changes in nitrate binding with lanthanides in BLPhen complexes
Preorganized ligands such as bis-lactam-1,10-phenanthroline (BLPhen) offer unique selectivity trends in solvent extraction of rare-earth ions, particularly from aqueous nitrate solutions. However, due to the ligand’s lipophilicity it is experimentally challenging to obtain crystal structures of the corresponding lanthanide (Ln):ligand complexes to describe the local structure of the first coordination shell and the role of the nitrate ions in the organic phase. In this work, we report first principles molecular dynamics (FPMD) simulations of the complexation of trivalent lanthanide ions (La, Nd, and Eu) with the BLPhen ligand in the presence of nitrate ions in the dichloroethane (DCE) solvent. We find that two nitrate anions are present in the first solvation shell and the third nitrate anion is far from the first solvation shell in all three [Ln(BLPhen) 2 ] 3+ complexes examined. Moving along the lanthanide series from La to Nd to Eu, the binding pocket formed by the two BLPhen ligands shrinks in size; as a result, the two nitrate configuration changes from one-monodentate/one-bidentate binding mode for La and Nd to all monodentate for Eu. Meanwhile, the total coordination number drops from 11 for La and Nd to 10 for Eu. More interestingly, the bidentate binding in [La(BLPhen) 2 ] 3+ and [Nd(BLPhen) 2 ] 3+ complexes is highly dynamic, frequently switching to monodentate and back. The FPMD insights into the differing modes and dynamics of nitrates in the first coordination shell will be useful for further atomistic understanding of the complex structure, formation, and stability in the organic phase.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A Polymer-Assisted Spinodal Decomposition Strategy toward Interconnected Porous Sodium Super Ionic Conductor-Structured Polyanion-Type Materials and Their Application as a High-Power Sodium-Ion Battery Cathode
A general polymer-assisted spinodal decomposition strategy is used to prepare hierarchically porous sodium super ionic conductor (NASICON)-structured polyanion-type materials (e.g., Na 3 V 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 , K 3 V 2 (PO 4 ) 3 , Na 4 MnV(PO 4 ) 3 , and Na 2 TiV(PO 4 ) 3 ) in a tetrahydrofuran/ethanol/H 2 O synthesis system. Depending on the boiling point of solvents, the selective evaporation of the solvents induces both macrophase separation via spinodal decomposition and mesophase separation via self-assembly of inorganic precursors and amphiphilic block copolymers, leading to the formation of hierarchically porous structures. We find that the resulting hierarchically porous Na 3 V 2 (PO 4 ) 3 possessing large specific surface area (≈77 m 2 g -1 ) and pore volume (≈0.272 cm 3 g -1 ) shows a high specific capacity of 117.6 mAh g -1 at 0.1 C achieving the theoretical value and a long cycling life with 77% capacity retention over 1000 cycles at 5 C. This method presented here can open a facile avenue to synthesize other hierarchically porous polyanion-type materials.
36 MATERIALS SCIENCE↗
Chemical recycling of mixed textile waste
Globally, less than 0.5% of postconsumer textile waste is recycled, with the majority incinerated or ending up in landfills. Most postconsumer textiles are mixed fibers, complicating mechanical recycling due to material blends and contaminants. Here, we demonstrate the chemical conversion of postconsumer mixed textile waste using microwave-assisted glycolysis over a ZnO catalyst followed by solvent dissolution. This approach electrifies the process heat while allowing rapid depolymerization of polyester and spandex to their monomers in 15 minutes. A simple solvent dissolution enables the separation of cotton and nylon. We assess the quality of all components through extensive material characterization, discuss their potential for sustainable recycling, and provide a techno-economic analysis of the economic feasibility of the process.
Science & Technology - Other Topics↗