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Flow-induced non-equilibrium conditions yielded high-purity Dy precipitate from aqueous mixtures of NdCl 3 and DyCl 3 more quickly compared to conventional equilibrium stirred mixing.
Although xylo-oligosaccharides production from lignocelluloses via lactic acid hydrolysis is advantageous in terms of high yields with less by-products, the use of high purity lactic acid inevitably increases the cost of xylo-oligosaccharides production. The utilization of lactic acid-rich fermentation broth for xylo-oligosaccharides production can avoid the separation and purification of lactic acid. However, the feasibility of lactic acid-rich fermentation broth for xylo-oligosaccharides production from lignocelluloses was unclear. In this work, the results indicated that the highest xylo-oligosaccharides yield of 72% was obtained from corncob by lactic acid-rich fermentation broth pretreatment and xylanase hydrolysis. Subsequently, monosaccharides-rich hydrolysate (90.9 g/L) was obtained from solid residues of corncob by cellulase hydrolysis. Lactic acid-rich fermentation broth was produced by Weizmannia coagulans fermentation of the monosaccharide-rich hydrolysate. Besides, the obtained xylo-oligosaccharides and lactic acid mixture might be used as feed additives, avoiding the purification and separation of lactic acid or xylo-oligosaccharides. Meanwhile, the production cost of feed grade xylo-oligosaccharides from this work was much lower than the current market price. Overall, this work proposed a new strategy for efficient and environmental-friendly production of xylo-oligosaccharides from corncob.
Astatine is one of the least chemically studied elements and its behavior in the presence of non- conventional solvents has not been investigated before. This work considers both hydrophobic ionic liquids and binary mixtures as alternatives to conventional solvents. The study is based on the extraction of astatine and bismuth (target material required to produce astatine) into imidazolium-based ionic liquid, and binary mixtures formed by active pharmaceuticals (ibuprofen, lidocaine) and a food grade ingredient (methyl anthranilate). It is shown that both the ionic liquid and binary mixtures can successfully extract At from nitric acid media, but extraction of Bi into the ionic liquid is very inefficient, resulting in a good separation factor for these two elements in the entire studied acidity range. Extraction of At into binary mixtures is very efficient, having distribution ratio values as high as 1000, while the behavior of Bi under these conditions depends on the composition of the mixture. Furthermore, a mathematical model has been developed to fit both At and Bi experimental data and applied to determine corresponding thermodynamic extraction constants.
Abstract Many industrial separations of chemically‐similar elements are achieved by solvent extraction, exploiting differences in speciation and solubility across aqueous‐organic interfaces. We recently identified [OM 4 (OH) 6 (SCN) 12 ] 4− (OM 4 , M=Zr/Hf IV ) tetrahedral oxoclusters as the main species in industrial processes that produce nuclear‐grade Zr and Hf from crude ore. However, isostructural/isoelectronic OM 4 ‐oxoclusters do not explain selective extraction of Hf into the organic phase. Here we have characterized heterometal Hf−Zr clusters in solution and the solid‐state yielding key information about their fundamentally different chemistry that engenders separation. Clusters prepared with both ammonium (industrial process) and tetramethylammonium counter cations revealed that 1) heterometal clusters (instead of a mixture of homometal clusters) assemble, and 2) Hf‐rich OM 4 selectively precipitates over Zr‐rich OM 4 , providing a separation process that does not require an organic extractant. Mass spectrometry, small‐angle X‐ray scattering, solution‐state 1 H nuclear magnetic resonance (NMR) spectroscopy, and solid‐state 17 O NMR evidence both mixed‐metal speciation and selective Hf‐precipitation. Raman spectroscopy suggests greater Zr‐ligand lability than Hf‐ligand lability, consistent with higher aqueous solubility of Zr‐rich clusters, enabling both extraction and precipitation‐based separation. Fundamentally, we also identify a key difference between these chemically similar elements that has enabled diversification of Zr‐polyoxocation chemistry over the last decade, while Hf‐polyoxocation chemistry lags.
In this work, we present indirect measurements of size-resolved ultrafine particle composition conducted during the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) Campaign in Utqiagvik, Alaska, during March 2009. This study focuses on measurements of size-resolved particle hygroscopicity and volatility measured over two periods of the campaign. During a period that represents background conditions in this location, particle hygroscopic growth factors (HGF) at 90% relative humidity ranged from 1.45 to 1.51, which combined with volatility measurements suggest a mixture of ~30% ammoniated sulfates and ~70% oxidized organics. Two separate regional ultrafine particle growth events were also observed during this campaign. Event 1 coincided with elevated levels of H2SO4 and solar radiation. These particles were highly hygroscopic (HGF = 2.1 for 35 nm particles), but were almost fully volatilized at 160 °C. The air masses associated with both events originated over the Arctic Ocean. Event 1 was influenced by the upper marine boundary layer (200–350 m AGL), while Event 2 spent more time closer to the surface (50–150 m AGL) and over open ocean leads, suggesting marine influence in growth processes. Event 2 particles were slightly less hygroscopic (HGF = 1.94 for 35 nm and 1.67 for 15 nm particles), and similarly volatile. We hypothesize that particles formed during both events contained 60–70% hygroscopic salts by volume, with the balance for Event 1 being sulfates and oxidized organics for Event 2. These observations suggest that primary sea spray may be an important initiator of ultrafine particle formation events in the Arctic late-winter, but a variety of processes may be responsible for condensational growth.
Aromatic polycarboxylic acids complex with imidazoles, forming supramolecular assemblies. Herein, we demonstrate that polybenzimidazole (PBI) can be augmented by aromatic polycarboxylic acids, including phthalic acid (PA), trimesic acid (TMA), and pyromellitic acid (PMA), and the resulting supramolecular assemblies exhibit attractive H 2 /CO 2 separation performance for precombustion carbon capture. The acid doping decreases the free volume and gas permeability but increases H 2 /CO 2 selectivity, which can be correlated with the molar ratio of the protons to PBI repeating units in the assemblies. Increasing the temperature decreases the H 2 /CO 2 selectivity because of weakened interactions. When challenged with model gas mixtures, a supramolecular assembly based on TMA shows H 2 /CO 2 separation properties superior to state-of-the-art materials and above Robeson's upper bound. Furthermore, this study elucidates the fruitful harnessing of dynamic non-covalent bonds to design robust and highly selective membranes for industrial gas separations.
Hydrogen can be used to reduce carbon emissions by blending into other gaseous energy carriers, such as natural gas. However, hydrogen blending into natural gas has important implications for safety which need to be evaluated. Hydrogen has different physical properties than natural gas, and these properties affect safety evaluations concerning a leak of the blended gas. The intent of this report is to begin to investigate the safety implications of blending hydrogen into the natural gas infrastructure with respect to a leak event from a pipeline. A literature review was conducted to identify existing data that will better inform future hazard and risk assessments for hydrogen/natural gas blends. Metrics with safety implications such as heat flux and dispersion behavior may be affected by the overall blend ratio of the mixture. Of the literature reviewed, there was no directly observed separation of the hydrogen from the natural gas or methane blend. No literature was identified that experimentally examined unconfined releases such as concentration fields or concentration at specific distances. Computational efforts have predicted concentration fields by modified versions of existing engineering models, but the validation of these models is limited by the unavailability of literature data. There are multiple literature sources that measured flame lengths and heat flux values, which are both relevant metrics to risk and hazard assessments. These data can be more directly compared to the outputs of existing engineering models for validation.
The present disclosure generally relates to apparatuses, systems, and methods for separating a target species (e.g., CO 2 ) from a gas mixture (e.g., gas stream) via an electrochemical process.
Metal–organic frameworks (MOFs) can efficiently purify hydrocarbons from CO 2 , but their rapid saturation, driven by preferential hydrocarbon adsorption, requires energy-intensive adsorption–desorption processes. To address these challenges, an innovative approach is developed, enabling control over MOF flexibility through densification and defect engineering, resulting in an intriguing inverse CO 2 /C2 hydrocarbon selectivity. Here, in this study, the densification process induces the shearing of the crystal lattice and contraction of pores in a defective CuBTC MOF. These changes have led to a remarkable transformation in selectivity, where the originally hydrocarbon-selective CuBTC MOF becomes CO 2 -selective. The selectivity values for densified CuBTC are significantly reversed when compared to its powder form, with notable improvements observed in CO 2 /C 2 H 6 (4416 vs 0.61), CO 2 /C 2 H 4 (15 vs 0.28), and CO 2 /C 2 H 2 (4 vs 0.2). The densified material shows impressive separation, regeneration, and recyclability during dynamic breakthrough experiments with complex quinary gas mixtures. Simulation studies indicate faster CO 2 passage through the tetragonal structure of densified CuBTC compared to C 2 H 2 . Experimental kinetic diffusion studies confirm accelerated CO 2 diffusion over hydrocarbons in the densified MOF, attributed to its small pore window and minimal interparticle voids. This research introduces a promising strategy for refining existing and future MOF materials, enhancing their separation performance.
High-resolution ion mobility spectrometry-mass spectrometry (HR-IMS-MS) instruments have enormously advanced the ability to characterize complex biological mixtures. Unfortunately, HR-IMS and HR-MS measurements are typically performed independently due to mismatches in analysis time scales. Here we overcome this limitation by using a dual-gated ion injection approach to couple an 11-meter path length structures for lossless ion manipulations (SLIM) module to a Q-Exactive Plus Orbitrap MS. The dual-gate setup was implemented by placing one ion gate before the SLIM module and a second ion gate after. The dual-gated ion injection approach allowed the new SLIM-Orbitrap platform to simultaneously perform an 11-meter SLIM separation, Orbitrap mass analysis using the highest selectable mass resolution setting (up to 140k), and high-energy collision induced dissociation (HCD) in ~25 minutes over an $m/z$ range of ~1500 amu. The SLIM-Orbitrap was initially characterized using a mixture of standard phosphazene cations and demonstrated an average SLIM CCS resolving power (Rp CCS ) of ~218 and SLIM peak capacity of ~156 while simultaneously obtaining high mass resolutions. SLIM-Orbitrap analysis with fragmentation was then performed on mixtures of standard peptides and two reverse peptides (SDGRG 1+ , GRGDS 1+ , Rp CCS = 305) to demonstrate the utility of combined HR-IMS-MS/MS measurements for peptide identification. Our new HR-IMS-MS/MS capability was further demonstrated by analyzing a complex lipid mixture and showcasing SLIM separations on isobaric lipids. In conclusion, this new SLIM-Orbitrap platform demonstrates a critical new capability for proteomics and lipidomics applications, and the high-resolution multimodal data obtainable with this system establishes the foundation for reference-free identification of unknown ion structures.
Rapid expansion of the unconventional oil and gas extraction has increased American energy independence, but also led to increased production of large amounts of contaminated water. Wastewater from the oil and gas industry contains a wide range of contaminants. Injecting such contaminated water into disposal wells or discharging it to the environment jeopardizes freshwater resources. Conventional and membrane-based wastewater treatment techniques are often not effective choices to treat highly contaminated wastewater; however, a suitable way to remove contaminants from wastewater is to selectively separate water in a process analogous to humidification-dehumidification (HDH). Only a few studies have investigated the use of HDH for wastewater treatment. In this study, a novel HDH system is introduced for treating highly contaminated water, such as oil and gas flowback and produced water. In this HDH process, a non-condensable gas, such as air, mixes with wastewater vapor to facilitate the separation of contaminants. As a result, clean water condenses from the multicomponent gaseous mixture while air carries organic contaminants out of the dehumidification section. A laboratory apparatus was constructed and experiments were performed to investigate the HDH process for wastewater treatment and to study the effects of flow dynamics including air flow rate on the composition of treated water. Different contaminants including benzene, toluene, 2-propanol and 2-butoxyethanol were tested. Experimental results showed that the system can be successfully applied for removing volatile and/or toxic organic contaminants from wastewater. A representative multicomponent mixture of fracking wastewater was successfully treated using the experimental setup and clean water with quality of 98.3% was obtained. It was revealed that increasing the air-to-vapor mass ratio improves purity of treated water. Quantitative analysis showed that by increasing the air-to-vapor mass ratio from 0.6 to 5.9, the fraction of separated 2-propanol through the air was improved from 43% to more than 96% of the initial amount. ASPEN software was employed to simulate equilibrium conditions. Finally, experimental results were observed to have lower mass fraction of residual contaminant in the treated water compared to equilibrium state.
The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.
Abstract Because C 2 H 4 plays an essential role in the chemical industry, economical and energy‐efficient separation of ethylene (C 2 H 4 ) from ethane (C 2 H 6 ) is extremely important. With the exception of energy‐intensive cryogenic distillation, there are few one‐step methods to obtain polymer‐grade (≥99.95 % pure) C 2 H 4 from C 2 H 4 /C 2 H 6 mixtures. Here we report a highly stable metal‐organic‐framework (MOF) FJI‐H11‐Me(des) (FJI‐H=Hong's group in Fujian Institute of Research on the Structure of Matter) which features one‐dimensional hexagonal nonpolar pore surfaces constructed by aromatic rings and alkyl groups. This FJI‐H11‐Me(des) adsorbs C 2 H 6 rather than C 2 H 4 between 273 and 303 K. Practical breakthrough experiments with C 2 H 4 containing 1 % C 2 H 6 have shown that FJI‐H11‐Me(des) can realize the acquisition in one‐step of polymer‐grade, 99.95 % pure C 2 H 4 under various conditions including different gas flow rates, temperatures and relative humidity.
The detection of hydrogen in complex gas mixtures is essential for many applications. Conventional approaches such as gas chromatography (GC) with thermal conductivity detection (TCD) and residual gas analyzers (RGAs) face significant limitations: TCD exhibits poor response when helium is used as a carrier gas, whereas RGAs lack chromatographic separation, preventing reliable quantification of hydrogen because of interference from other species. Traditional GC methods rely on dual-column configurations with packed or molecular-sieve porous layer open tubular (PLOT) columns to separate hydrogen from O2, N2, CO, CO2, CH4, and other hydrocarbons, increasing system complexity and limiting compatibility with mass spectrometry (MS) detection. In this work, we developed and validated a robust GC–MS method capable of directly detecting and quantifying hydrogen using electron ionization (EI) without dopants, reagent gases, or ion–molecule reaction schemes. By integrating a modified EI source and a cryogenically cooled single capillary column configuration, we achieved baseline separation of hydrogen from all major permanent gases and hydrocarbons in a refinery gas mixture using helium as the carrier gas. The method demonstrated excellent linearity, high sensitivity, and exceptional reproducibility. Adjustable sample-loop volumes and split ratios enabled optimization of peak shape and signal-to-noise performance for trace-level and percent-level hydrogen concentrations. Beyond hydrogen quantitation, the method provides simultaneous compositional profiling of other gases in a mixture in a single run, making it valuable for a wide range of tasks.
Understanding mass transport mechanisms in nanopores is important for developing advanced materials for chemical separations, chemical sensing, and energy storage. This paper reports a novel imaging platform that is employed for the first time to investigate the detailed diffusion dynamics of single rhodamine B (RhB) dye molecules confined within solution-filled cylindrical anodic aluminum oxide (AAO) nanopores. The imaging platform relies on illumination of horizontally-oriented AAO nanopores in a highly inclined and laminated optical (HILO) light sheet microscopy geometry. The method was used to investigate the translational and orientational dynamics of single rhodamine B (RhB) molecules within horizontally-oriented 5- and 10-nm diameter AAO nanopores filled with water–ethanol mixtures. The established platform enabled the observation of one-dimensional motion along the pore axis involving occasional short- or long-term immobilization at the single-molecule level. Analysis of cumulative squared-displacement distributions revealed fast (5 – 30 µm²/s), intermediate (1 – 5 µm²/s), and slow (< 1 µm²/s) diffusion components. From the effects of mixture composition and pore size on the contributions of these three components, we inferred that the fast, intermediate, and slow components could be assigned to desorption-mediated hopping, crawling, and wiggling motions, respectively. The platform based on the horizontally-oriented AAO nanopores also permitted single-molecule emission polarization measurements that revealed the negligible steric confinement of individual diffusing RhB molecules within the AAO nanopores. The imaging platform based on AAO membranes and HILO microscopy provided a unique means to investigate how solvation-mediated surface interactions and nanoconfinement govern molecular transport in nanoporous environments.
Methods for separating Ra from Pb, Bi, and Th are provided, the methods can include: providing a first mixture comprising Ra, Pb, Bi, and/or Th; providing a system that can include: a first vessel housing a first media; a second vessel in fluid communication with the first vessel, the second vessel housing a second media; and a third vessel in fluid communication with the second vessel, the third vessel housing a third media; and exposing the first mixture to the first media within the first vessel then, through the fluid communication, exposing the first remainder to the second media in the second vessel, then, through fluid communication, exposing the next remainder to the third media in the third vessel, the exposing separating the Th and Bi from the Ra and Pb, and the Ra from the Pb. Methods for separating Ra from being associated with a media are also provided. The methods can include: exposing the Ra and media to a chelating agent to form a mixture comprising the Ra complexed with the chelating agent.
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.
Here the trapping of paraffins is beneficial compared to selective olefin adsorption for adsorptive olefin purification from a process engineering point of view. Here we demonstrate the use of a series of Zn 2 (X-bdc) 2 (dabco) (where X-bdc 2- is bdc 2- = 1,4-benzenedicarboxylate with substituting groups X, DM-bdc 2- = 2,5-dimethyl-1,4-benzenedicarboxylate or TM-bdc 2- = 2,3,5,6-tetramethyl-1,4-benzenedicarboxylate and dabco = diazabicyclo[2.2.2.]octane) metal-organic frameworks (MOFs) for the adsorptive removal of ethane from ethylene streams. The best performing material from this series is Zn2(TM-bdc)2(dabco) (DMOF-TM), which shows a high ethane uptake of 5.31 mmol g -1 at 110 kPa, with a good IAST selectivity of 1.88 towards ethane over ethylene. Through breakthrough measurements a high productivity of 13.1 L/kg per breakthrough is revealed with good reproducibility over five consecutive cycles. Molecular simulations show that the methyl groups of DMOF-TM are forming a van der Waals trap with the methylene groups from dabco, snuggly fitting the ethane. Further, rarely used high pressure coadsorption measurements, in pressure regimes that most scientific studies on hydrocarbon separation on MOFs ignore, reveal an increase in ethane capacity and selectivity for binary mixtures with increased pressures. The coadsorption measurements reveal good selectivity of 1.96 at 1000 kPa, which is verified also through IAST calculations up to 3000 kPa. This study overall showcases the opportunities that pore engineering by alkyl group incorporation and pressure increase offer to improve hydrocarbon separation in reticular materials.