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Promising advances in membrane technology can lead to energy-saving and eco-friendly solutions in industrial sectors. This work demonstrates a highly selective membrane with ultrathin and highly interconnected organosiloxane polymer nanolayers by initiated chemical vapor deposition to effectively separate solutes within the molecular weight range of 150-300 g mol-1. We optimize the poly(1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) membrane by adjusting both the thickness of the selective layer and the pore sizes of its support membranes. Notably, the 29 nm selective layer imparts a uniformly narrow molecular sieving property, providing a record-high solute-solute selectivity of 39.88 for different-sized solutes. Furthermore, a solute-solute selectivity of 11.04 was demonstrated using the real-world active pharmaceutical ingredient mixture of Acyclovir and Valacyclovir, key components for Herpes virus treatment, despite their molecular weight difference of less than 100 g mol-1. The highly interconnected membrane is expected to meet rigorous requirements for high-standard active pharmaceutical ingredient separation.
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Recently, weather data have been applied to one of deep learning techniques known as "long short-term memory (LSTM)" to predict streamflow in rainfall-runoff relationships. However, this approach may not be suitable for regions with artificial water management structures such as dams and weirs. Therefore, this study aims to evaluate the prediction accuracy of LSTM for streamflow depending on the availability of dam/weir operational data across South Korea. Four scenarios were prepared for 25 streamflow stations. Scenarios #1 and #2 used weather data and weather and dam/weir operational data, respectively, with the same LSTM model conditions for all stations. Scenarios #3 and #4 used weather data and weather and dam/weir operational data, respectively, with the different LSTM models for individual stations. The Nash-Sutcliffe efficiency (NSE) and the root mean squared error (RMSE) were adopted to assess the LSTM's performance. The results indicated that the mean values of NSE and RMSE were 0.277 and 292.6 (Scenario #1), 0.482 and 214.3 (Scenario #2), 0.410 and 260.7 (Scenario #3), and 0.592 and 181.1 (Scenario #4), respectively. Overall, the model performance was improved by the addition of dam/weir operational data, with an increase in NSE values of 0.182-0.206 and a decrease in RMSE values of 78.2-79.6. Surprisingly, the degree of performance improvement varied according to the operational characteristics of the dam/weir, and the performance tended to increase when the dam/weir with high frequency and great amount of water discharge was included. Our findings showed that the overall LSTM prediction of streamflow was improved by the inclusion of dam/weir operational data. When using dam/weir operational data to predict streamflow using LSTM, understanding of their operational characteristics is important to obtain reliable streamflow predictions.
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Tiempo (Meteorología) , República de CoreaRESUMEN
For ethylene/ethane separation, a CMS (carbon molecular sieve) membrane was developed with a PAN (polyacrylonitrile) polymer precursor on an alumina support. To provide an excellent thermal property to PAN precursor prior to the pyrolysis, the stabilization as a pre-treatment process was carried out. Tuning the stabilization condition was very important to successfully preparing the CMS membrane derived from the PAN precursor. The stabilization and pyrolysis processes for the PAN precursor were finely tuned, and optimized in terms of stabilization temperature and time, as well as pyrolysis temperature, heating rate, and soaking time. The PAN stabilized at >250 °C showed improved thermal stability and carbon yield. The CMS membrane derived from stabilized PAN showed reasonable separation performance for ethylene permeance (0.71 GPU) and ethylene/ethane selectivity (7.62), respectively. Increasing the pyrolysis temperature and soaking time gave rise to an increase in the gas permeance, and a reduction in the membrane selectivity. This trend was opposite to that for the CMS membranes derived from other polymer precursors. The optimized separation performance (ethylene permeance of 2.97 GPU and ethylene/ethane selectivity of 7.25) could be achieved at the pyrolysis temperature of 650 °C with a soaking time of 1 h. The separation performance of the CMS membrane derived from the PAN precursor was comparable to that of other polymer precursors, and surpassed them regarding the upper bound trade off.
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Metal-organic frameworks (MOFs) are a class of microporous materials that have been highlighted with fast and selective sorption of gas molecules; however, they are at least partially unstable in the scale-up process. Here, we report a rational shaping of MOFs in a scalable architecture of fiber sorbent. The long-standing stability challenge of MOFs was resolved by using stable metal oxide precursors that are subject to controlled surface oxide dissolution-growth chemistry during the Mg-based MOF synthesis. Highly uniform MOF crystals are synthesized along with the open-porous fiber sorbents networks, showing unprecedented cyclic CO2 capacities in both flue gas and direct air capture (DAC) conditions. The same chemistry enables an in situ flow synthesis of Mg-MOF fiber sorbents, providing a scalable pathway for MOF synthesis in an inert condition with minimal handling steps. This modular approach can serve both as a reaction stage for enhanced MOF fiber sorbent synthesis and as a "process-ready" separation device.
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Carbon molecular sieve (CMS) membranes have been developed to replace or support energy-intensive cryogenic distillation for olefin/paraffin separation. Olefin and paraffin have similar molecular properties, but can be separated effectively by a CMS membrane with a rigid, slit-like pore structure. A variety of polymer precursors can give rise to different outcomes in terms of the structure and performance of CMS membranes. Herein, for olefin/paraffin separation, the CMS membranes derived from a number of polymer precursors (such as polyimides, phenolic resin, and polymers of intrinsic microporosity, PIM) are introduced, and olefin/paraffin separation properties of those membranes are summarized. The effects from incorporation of inorganic materials into polymer precursors and from a pyrolysis process on the properties of CMS membranes are also reviewed. Finally, the prospects and future directions of CMS membranes for olefin/paraffin separation and aging issues are discussed.
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Data assimilation (DA) techniques are powerful means of dynamic natural system modeling that allow for the use of data as soon as it appears to improve model predictions and reduce prediction uncertainty by correcting state variables, model parameters, and boundary and initial conditions. The objectives of this review are to explore existing approaches and advances in DA applications for surface water quality modeling and to identify future research prospects. We first reviewed the DA methods used in water quality modeling as reported in literature. We then addressed observations and suggestions regarding various factors of DA performance, such as the mismatch between both lateral and vertical spatial detail of measurements and modeling, subgrid heterogeneity, presence of temporally stable spatial patterns in water quality parameters and related biases, evaluation of uncertainty in data and modeling results, mismatch between scales and schedules of data from multiple sources, selection of parameters to be updated along with state variables, update frequency and forecast skill. The review concludes with the outlook section that outlines current challenges and opportunities related to growing role of novel data sources, scale mismatch between model discretization and observation, structural uncertainty of models and conversion of measured to simulated vales, experimentation with DA prior to applications, using DA performance or model selection, the role of sensitivity analysis, and the expanding use of DA in water quality management.
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Modelos Teóricos , Calidad del Agua , Predicción , IncertidumbreRESUMEN
In order to find an alternative for classical distillation in the recovery of ECH/IPA from azeotropic ECH/IPA/water (50/30/20 w/w, %) mixtures, a pervaporation process has been applied. Membranes from the crosslinking of poly(vinyl alcohol)/poly(vinyl amine) (PVA/PVAm) were prepared, and then the membrane stability and pervaporation efficiency of the crosslinked PVA/PVAm membranes were studied for highly reactive ECH systems containing a ternary feed mixture. From the Fourier-transform infrared (FT-IR) spectroscopy analysis, it was observed that all of the membranes were chemically stable for 15 days of immersion in a 50 : 30 : 20 ECH/IPA/water (w/w, %) feed mixture at 60 °C. The degree of membrane swelling increased with increasing PVAm content in the membrane composition, water content in the feed composition, and feed temperature, which was attributed to the increase in the number of hydrophilic sites in the membrane. The field-emission scanning electron microscopy (FE-SEM) study revealed that higher PVAm content membranes (PVAm1.0 and PVAm1.5) show polymer phase extraction in ECH/IPA/water (50 : 30 : 20) (w/w, %) at 60 °C in long-term stability tests. The pervaporation dehydration characteristics for all of the membranes with the feed comprising an ECH/IPA/water (50 : 30 : 20 by weight) azeotropic mixture at 30 °C were examined and excellent pervaporation dehydration efficiency was found. Quantitatively, the flux increased from 0.025 to 0.32 kg (m2 h)-1 and the separation factor decreased from 1908 to 60 with increasing PVAm content in the blended membrane.
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Ag-exchanged NaY zeolite (Ag-NaZ) particles were prepared by ion exchange and introduced to a polyvinyl alcohol (PVA) membrane cross-linked with polyacrylic acid (PAA) for the pervaporation dehydration of an isopropanol (IPA) aqueous mixture. The Ag-exchanged NaY zeolite particles were characterized by FE-SEM, EDS, BET, and XRD studies. The prepared Ag-NaZ-loaded PVA/PAA composite membrane was characterized by FE-SEM, XRD, a swelling study, and contact angle measurements. Pervaporation characteristics were investigated in terms of Ag-NaZ concentrations within PVA/PAA membranes using diverse feed solution conditions. The preferential sorption of IPA/water mixtures for Ag-NaZ-introduced membranes were also determined by calculating the apparent activation energies of IPA and water permeation, respectively. As a result, flux and selectivity increased with the Ag-NaZ concentration to 5 wt% in the membrane. Optimum pervaporation performance was observed in a 5 wt% Ag-NaZ-incorporated membrane with a flux equal to 0.084 kg m-2 h-1 and a separation factor of 2717.9 at 40 °C from an 80 wt% IPA aqueous feed solution.