Advancing the Productivity-Selectivity Trade-off of Temperature Swing Solvent Extraction Desalination with Intermediate-Step Release

Temperature swing solvent extraction (TSSE) offers a membrane-less and nonevaporative approach to hypersaline desalination, but performance of conventional TSSE operation is restricted by an inherent trade-off between water recovery yield and salt rejection. This study presents enhanced desalination capability of TSSE with a novel intermediate release step (TSSE-IR) over a conventional (c-TSSE) single-step operation. TSSE-IR demonstrated superior performance in the hypersaline desalination of 1.0 M NaCl brines for three amines with distinct water and salt partitioning behaviors: diisopropylamine, triethylamine, and tert-octylamine. The astute introduction of the intermediate temperature step in TSSE-IR dramatically improves salt rejection while minimizing the sacrifices in water recovery yields. We show that the intermediate step does not introduce additional solvent loss compared with c-TSSE operations with the same extraction temperature for any of the three solvents examined. TSSE-IR is demonstrated to advance the productivity-selectivity trade-off that constrains c-TSSE. Finally, Hunter–Nash analysis conducted on diisopropylamine–H2O–NaCl ternary diagrams exhibits good agreement with experimental TSSE-IR results, offering a reliable platform for modeling intermediate-step release performance and informing process design. This study establishes the potential of TSSE-IR to expand the spectrum of viable solvents for hypersaline desalination to include greener chemicals that exhibit high water recovery yields but low selectivities in c-TSSE

Phase equilibria insights into amine-water-NaCl interactions in liquid-liquid biphasic systems for temperature swing solvent extraction desalination

This study sheds light on the fundamental phenomena governing temperature swing solvent extraction (TSSE) desalination by investigating the influence of temperature on the equilibrium partitioning of water, salt, and solvent. The distribution of components across a range of temperatures and feed salinities typical to TSSE hypersaline desalination was examined for two amine solvents. A tradeoff between selectivity and productivity is established, providing a novel framework to assess TSSE performance. Salt was shown to be a key determinant in equilibrium partitioning by diminishing the ability of the solvent to extract water at lowered temperatures and salting-out amines from the aqueous phase. Na+ and Cl− ions consistently partition into the solvent phase in equimolar ratios. Analysis further reveals a linear correlation between the natural logarithms of salt activity coefficients and water contents of the organic phase. The two collaborating results suggest that water-ion interactions are more important than amine-ion interactions in the organic phase, resolving a critical gap in the understanding of salt transport. The findings of this study can provide important insights for the informed development of temperature swing solvent extraction for hypersaline desalination

Assessing the Temperature-Dependent Tunable Polarity of N,N‑Dimethylcyclohexylamine (DMCHA) and Water Mixtures

The promise of switchable solvents as green solvent alternatives lies in the ability to drastically alter their properties based on an external trigger. Switchable hydrophilicity solvent N,N-dimethylcyclohexylamine, DMCHA, is known to change properties based on both CO2 addition and variations in temperature, both in the presence of water. While the impact of temperature has been observed via changes in water solubility, the solvent properties underlying these observations have not been quantified. Kamlet–Taft solvatochromic parameters (α, β, and π*) and dielectric constants for DMCHA and DMCHA–water mixtures were measured across a temperature range of 25–60 °C. Temperature swing effects of DMCHA in addition to CO2-switching capabilities were validated and quantified on the Kamlet–Taft polarity scale. Notably, binary mixtures of water in DMCHA show promising tunability in terms of its β and π* parameters induced by moderate variations in temperature. Potential applications for this CO2-switchable and temperature-tunable solvent are discussed

Solvent-driven aqueous separations for hypersaline brine concentration and resource recovery

Solvent-driven separation processes can extract water and high-value minerals from high salinity or contaminated brines, simultaneously reducing the environmental impact of brine disposal and enabling resource recovery. The efficient dewatering of hypersaline brines is essential for the sustainable minimal and zero liquid discharge processing of industrial wastewaters. Fractional crystallization can selectively extract ions from contaminated waste streams, allowing critical materials to be recycled, including transition and lanthanide metals required for renewable energy generation and storage. Mass transfer in solvent-driven water extraction occurs across a liquid–liquid interface, eliminating the scaling and fouling of membrane and heat exchanger surfaces and limiting the need for extensive pretreatment. Solvent-driven fractional crystallization can leverage sequential treatment and control of process conditions to rapidly recover salts without requiring evaporation of water. Despite promising applications, the principles and potential of solvent-driven aqueous separations remain poorly understood. This critical review explores the opportunities presented by solvent-based aqueous separations from the molecular to process scale, evaluating the chemistry of solvation and system design in the broader context of desalination, resource recovery, water softening, and mineral production

Computational and experimental study of different brines in temperature swing solvent extraction desalination with amine solvents

Rapid global urbanization and high-salinity wastewater disposal from industrial activities have exerted significant pressure on water resources. Over the past few years, temperature swing solvent extraction (TSSE) has been identified as a promising technique to desalinate hypersaline brines. Despite its potential, the TSSE desalination literature has been mainly based on empirical insights, and the limited molecular simulation studies have primarily focused on NaCl brines. Herein, we use molecular dynamics (MD) simulations to study the TSSE desalination of four different brines, namely, KCl, KBr, NaCl, and NaBr using diisopropylamine as the solvent. Based on both bulk and interfacial brine-diisopropylamine MD results, we investigate the qualitative and quantitative performance of the simulations by benchmarking these results against our experimental evaluations of these same systems. MD results provide satisfactory qualitative agreement with the experimental data of water solubilization in the organic phase and amine solubilization in the aqueous phase for the KBr, KCl, and NaBr brines. Also, the molecular mechanism of solvation of ionic species by water molecules over diisopropylamine suggested by the MD simulations is in agreement with our experimental data. However, larger qualitative and quantitative deviations were observed for the NaCl brines, and this is likely due to polarization and charge transfer effects, as quantified by our quantum chemical calculations