Switchable carbamate coagulants to improve recycling ionic liquid from biomass solutions

There are many advantages to using ionic liquids as solvents or catalysts in chemical processes. Their non-volatile characteristic and high cost, however, can pose economic, environmental, and long-term health concerns. As such, the recovery and recycling of ionic liquids have become essential to mitigate their environmental impact and to reduce costs. Numerous recovery and recycling methods have been reported, including distillation, extraction, membrane separation (a.k.a. filtration), adsorption, crystallization, gravity, and electrochemical separation. Whereas most of these methods recover both cations and anions of the ionic liquid as ion pairs, recycling methods such as single-phase ion exchange or mixed-ion exchange/non-ionic adsorption methods recover only one of the ionic liquid ions, typically the cation. These methods are frequently used for the recycling of ionic liquids having simple anions such as chloride or acetate, but are seldom employed for ionic liquids consisting of larger and more complex anions due to the added time and reagent costs necessary for the regeneration of the original ionic liquid. Herein, a combined cation and anion exchange adsorption-desorption method is presented that can effectively separate 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonimide) [DMPIm][NTf2] ionic liquid from neutral impurities. More importantly, the method is capable of recovery and recycling of the original ionic liquid. Concomitant desorption of both ionic liquid ions was achieved using 0.1 M NaCl: methanol (90:10 v/v) eluent followed by isolation using liquid–liquid extraction to afford high purity products and yields of approximately 60%.

Assessing the recyclability of superbase-derived ionic liquids in cellulose processing: An insight from degradation mechanisms

Biomass pretreatment using certain ionic liquids (ILs), such as 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]), can be highly effective at reducing the recalcitrance of lignocellulosic biomass to enzymatic degradation. However, current commercial enzyme cocktails, derived from filamentous fungi and developed for dilute acid pretreatment, are inhibited by the most effective ILs used for pretreatment and require excessive amounts of water to remove the ILs from biomass after pretreatment in order to be effective. The associated IL recycling and waste disposal costs of this process pose significant economic and process engineering challenges for the commercial scale-up of IL pretreatment-based technologies. For the first time, we have demonstrated a one-pot, wash-free process that combines IL pretreatment and saccharification into a single vessel. After treating the switchgrass with [C2mim][OAc] and dilution with water to a final IL concentration of 10–20%, the pretreatment slurry was directly hydrolyzed using a thermostable IL tolerant enzyme cocktail previously developed at the Joint BioEnergy Institute (JBEI). This one-pot process liberated 81.2% glucose and 87.4% xylose (monomers and oligomers) at 72 h at 70 °C with an enzyme loading of 5.75 mg g−1 of biomass at 10% [C2mim][OAc]. Glucose and xylose were selectively separated by liquid–liquid extraction with over 90% efficiency, thus eliminating extensive water washing as a unit operation. This study opens avenues for developing more efficient and cost effective processes for product recovery and IL recycling.

In the present work, it was found that aqueous solution of a hydrophilic ionic liquid (IL), 1-butyl-3-methylimidazolium dicyanamide ([C4mim][N(CN)2]), could be separated into an aqueous two-phase system (ATPS) by inorganic salts such as K2HPO4 and K3PO4. The top phase is IL-rich, while the bottom phase is phosphate-rich. It was shown that 82.7%–100% bovine serum albumin (BSA) could be enriched into the top phase and almost quantitative saccharides (arabinose, glucose, sucrose, raffinose or dextran) were preferentially extracted into the bottom phase in a single-step extraction by [C4mim][N(CN)2] + K2HPO4 ATPS. The extraction efficiency of BSA from the aqueous saccharide solutions was influenced by the molecular structure of saccharides. The conductivity, dynamic light scattering (DLS) and transmission electron microscopy (TEM) were combined to investigate the microstructure of the IL-rich top phase and the possible mechanism for the selective separation. It is suggested that the formation of the IL aggregate and the IL aggregate-BSA complex plays a significant role in the separation of BSA from aqueous saccharide solutions. This is the first example for the selective separation by ILs-based ATPSs. It is expected that these findings would have potential applications in bio-analysis, separation, and IL recycle.

Insight into the interaction between arabinoxylan and imidazolium acetate-based ionic liquids

BackgroundLignocellulosic biorefineries have tonnage and throughput requirements that must be met year round and there is no single feedstock available in any given region that is capable of meeting the price and availability demands of the biorefineries scheduled for deployment. Significant attention has been historically given to agriculturally derived feedstocks; however, a diverse range of wastes, including municipal solid wastes (MSW), also have the potential to serve as feedstocks for the production of advanced biofuels and have not been extensively studied. In addition, ionic liquid (IL) pretreatment with certain ILs is receiving great interest as a potential process that enables fractionation of a wide range of feedstocks. Acid catalysts have been used previously to hydrolyze polysaccharides into fermentable sugars following IL pretreatment, which could potentially provide a means of liberating fermentable sugars from lignocellulose without the use of costly enzymes. However, successful optimization and scale-up of the one-pot acid-assisted IL deconstruction for further commercialization involve challenges such as reactor compatibility, mixing at high solid loading, sugar recovery, and IL recycling, which have not been effectively resolved during the development stages at bench scale.ResultsHere, we present the successful scale-up demonstration of the acid-assisted IL deconstruction on feedstock blends of municipal solid wastes and agricultural residues (corn stover) by 30-fold, relative to the bench scale (6 vs 0.2 L), at 10% solid loading. By integrating IL pretreatment and acid hydrolysis with subsequent centrifugation and extraction, the sugar and lignin products can be further recovered efficiently. This scale-up development at Advanced Biofuels/Bioproducts Process Demonstration Unit (ABPDU) will leverage the opportunity and synergistic efforts toward developing a cost-effective IL-based deconstruction technology by drastically eliminating enzyme, reducing water usage, and simplifying the downstream sugar/lignin recovery and IL recycling.ConclusionResults indicate that MSW blends are viable and valuable resource to consider when assessing biomass availability and affordability for lignocellulosic biorefineries. This scale-up evaluation demonstrates that the acid-assisted IL deconstruction technology can be effectively scaled up to larger operations and the current study established the baseline of scaling parameters for this process.

As opposed to ceramic methods, low-temperature solvothermal-hydrothermal methods using liquid media as reaction support are less energy demanding to design new electrode materials; therefore, they tend to replace ceramic routes. Here, we report the use of ionic liquids as both solvent and template to enable the growth of LiFePO4 (LFP) powders with controlled size and morphology at temperatures at least 200 °C lower than those required for conventional ceramic methods, while showing excellent electrochemical performances versus lithium. An inherent advantage to the use of ionic liquids lies in the feasibility of carrying out the reaction at atmospheric pressure. Besides, the recovery of the powders from the reacting medium is particularly easy, as are the effluents and ionic liquid recycling. Additionally, it is shown that ionic liquids can be used as a structural directing agent to orient crystal growth and obtain powders adopting a single morphology. Needless to say, such a new approach, which is not specific to LiFePO4, offers great opportunities for the low-temperature synthesis of new electrode materials.

Recent advances for sustainable production of levulinic acid in ionic liquids from biomass: Current scenario, opportunities and challenges

Two types of ionic liquids (halide anion ionic liquids and Bronsted acidic ionic liquids) were first applied to improve the palladium-catalyzed amidocarbonylation. Both the palladium catalyst and the ionic liquids could be recycled at least five times without significant loss in catalytic activity.

Recent global geopolitical tensions have exacerbated the scarcity of rare-earth elements (REEs), which are critical across many industries. REE-rich coal fly ash (CFA), a coal combustion residual, has been proposed as a potential source. Conventional REE-CFA recovery methods are energy- and material-intensive and leach elements indiscriminately. This study has developed a new valorization process based on the ionic liquid (IL) betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) for preferential extraction of REEs from different CFAs. Efficient extraction relies on [Hbet][Tf2N]'s thermomorphic behavior with water: upon heating, water and the IL form a single liquid phase, and REEs are leached from CFA via a proton-exchange mechanism. Upon cooling, the water and IL separate, and leached elements partition between the two phases. REEs were preferentially extracted over bulk elements from CFAs into the IL phase and then recovered in a subsequent mild-acid stripping step, regenerating the IL. Alkaline pretreatment significantly improved REE leaching efficiency from recalcitrant Class-F CFAs, and additional betaine improved REE and bulk element separation. Weathered CFA showed slightly higher REE leaching efficiency than unweathered CFA, and Class-C CFA demonstrated higher leaching efficiency but less selective partitioning than Class-F CFAs. Significantly, this method consistently exhibits a particularly high extraction efficiency for scandium across different CFAs.

Conductivity, viscosity, and thermodynamic properties of propylene carbonate solutions in ionic liquids

Ionic liquids (ILs) have great potential as solvents and catalysts in the most diverse areas of the chemical industry. However, the need for a process that allows the recycling and purification of ILs in an efficient and economically viable manner is restricting the practical application of these solvents. The recycling processes most used to recover ILs are distillation and evaporation, followed by extraction and crystallization. However, most of these processes demand high energy consumption, or temperatures that may compromise the structural and chemical stability of the ILs. This work focuses on understanding the separation of ionic liquid from aqueous solution using membranes, a technique widely used in industry. The separation of eleven ILs (([C4mim][AOc], [C4mim][SCN], [C4mim][CF3SO3], [C4mim][CF3CO2], [C4mim][Cl], [C8mim][Cl], [P4444][Cl], [N4444][Cl], [C4mpip][Cl], [C4mpyr][Cl] and [C4-2-mpy][Cl]) was studied using a nanofiltration (NF270) and a reverse osmosis (BW30LE) membrane. The influence of cation and anion, pressure, IL concentration, and temperature, on the separation of ILs, was evaluated. The Donnan exclusion mechanism was found to be the limiting factor for the reverse osmosis, while the combination of concentration polarization and sieving mechanism was the limiting factor for nanofiltration membrane. The increase of temperature and pressure leads to an increase in the volumetric flux at the cost of a decrease of the IL retention. On the other hand, the increase in the concentration of the IL solution resulted in an increase in the osmotic pressure and, consequently, a decrease in the volumetric flow and a decrease in the rejection of the IL.

Densities, viscosities and derived thermophysical properties of water-saturated imidazolium-based ionic liquids

The process of jatropha oil transesterification was studied for biodiesel production. Rhizomucor miehei lipase (RML) immobilized on 3-aminopropyltriethoxysilane functionalized magnetic Fe3O4 was employed as a biocatalyst. The immobilized lipase was confirmed by scanning electron microcopy (SEM), Fourier transform infrared spectra (FT-IR), thermogravimetric analysis (TGA), vibrating sample magnetometer (VSM), and confocal laser scanning microscopy (CLSM) techniques. The efficient biodiesel synthesis in ionic liquids using immobilized RML was demonstrated. Fifteen kinds of ionic liquids based on different alkyl chain lengths of the methyl imidazolium cation ([C2MIM], [C4MIM], [C8MIM], [C12MIM], and [C16MIM]) combined with [NTf2], [N(CN)2], [PF6] or [BF4] anions were assayed as reaction media for RML producing biodiesel. The highest synthetic activity of immobilized RML appeared in [BMIM][PF6], which is more than five times higher than the free enzyme. The enzyme catalytic activity remained 60% even after the magnetic nano-biocatalyst and ionic liquid had been reused 5 times in a 48-h reaction cycle. In addition, the immobilized enzyme exhibited excellent storage stability with almost no decrease in catalytic activity after storing at − 20 °C for 98 days.

One of the major concerns for utilizing ionic liquid on an industrial scale is the cost involved in the production. Despite its proven pretreatment efficiency, expenses involved in its usage hinder its utilization. A better way to tackle this limitation could be overcome by studying the recyclability of ionic liquid. The current study has applied the Box–Behnken design (BBD) to optimize the pretreatment condition of rice straw through the usage of 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) as an ionic liquid. The model predicted the operation condition with 5% solid loading at 128.4 °C for 71.83 min as an optimum pretreatment condition. Under the optimized pretreatment condition, the necessity of the best anti-solvent was evaluated among water, acetone methanol, and their combinations. The study revealed that pure methanol is the suitable choice of anti-solvent, enhancing the highest sugar yield. Recyclability of EMIM-Ac coupled with anti-solvent was conducted up to five recycles following the predicted pretreatment condition. Fermentation studies evaluated the efficacy of recycled EMIM-Ac for ethanol production with 89% more ethanol production than the untreated rice straw even after five recycles. This study demonstrates the potential of recycled ionic liquid in ethanol production, thereby reducing the production cost at the industrial level.