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Phase modifiers are low molecular weight molecules added to solvent extraction separations to improve the physical performance of the separation system, for example by increasing the concentration of metal ions that can be separated or improving the compatibility of the two solvents.
This report, prepared within Work package 1 of IEA Wind Task 49, presents reference site conditions for floating wind arrays to serve as a design basis for the techno-economic design of reference floating wind arrays. Data of the reference sites presented here are publicly available in an open database and thus support fast development and comparable design of floating wind arrays for various relevant conditions. The development of these reference sites drew on existing open access datasets and ongoing research projects of task participants. Six classes were identified that describe relevant key conditions for the design and development of floating wind arrays: met-ocean conditions, seabed conditions, coastal infrastructure, environmental impact, socio-economic impact, as well as regulations and permissions. The reference sites for the techno-economic design of floating wind arrays are based on a concept with building blocks to synthesize purpose-built site representations. In each of the identified classes with influencing design factors, building blocks are used to describe the characteristic properties and their spread. However, the latter three classes (i.e., environmental impact, socio-economic impact, regulations and permissions) are not included in the reference site conditions due to limited knowledge and lack of reliable criteria to quantify their impact on the techno-economic design in numeric parameters. Building blocks with key parameters for the techno-economic design of floating wind arrays are provided for met-ocean conditions, seabed conditions, and coastal infrastructure. For met-ocean conditions, multiple sites were selected for detailed analysis that represent a range of conditions across the pipeline of floating wind projects. Wind conditions and sea states are separated, and each location considers both the severity of wind and waves e.g. one site may have a moderate wave condition but severe wind condition. From this pipeline, eleven representative sites were selected where both site-specific analysis was available within the consortium, and where they represent different parts of the global pipeline. The eleven sites are: Hannibal (Italy), Humboldt (US), Ulsan (South Korea), MoneyPoint One (Ireland), Havbredey (UK), Fukushima (Japan), Utsira Nord (Norway), Gulf of Maine (US), Sud de la Bretagne II (France), Sorlige Nordsjo II (Norway). Each of these sites is summarized in the main report while more details about the studies and analyses behind the datasets are provided in the appendix. For seabed conditions, general information about the geotechnical parameters is provided and a baseline is established for the geotechnical parameters and stratigraphy that may be encountered on the sites. A set of six 'synthetic cases' is defined as building blocks providing the different parameters required for design under each case/soil condition. For the coastal infrastructure, general information about the main requirements is provided that a port should comply with to provide a satisfactory service during the construction of floating offshore wind arrays. Minimum port infrastructural requirements are provided for three types of ports.
Redox meditators (RMs) are soluble catalysts located in an electrolyte that can improve the energy efficiency (reduced overpotential) and cyclability of Li-oxygen (Li-O-2) batteries. In this work, 20 RMs within a Li-O-2 system with dimethyl sulfoxide and tetraethylene glycol dimethyl ether electrolytes are studied and their electrochemical features such as redox potential, the separation of cathodic and anodic peaks, and their current intensities are measured using cyclic voltammetry (CV) experiments. Six RMs are selected as "primary" choices based on their electrochemical performance, and stability tests are then performed to examine their electrochemical responses after consecutive cycles. Moreover, galvanostatic cycling tests are performed within a Li-O-2 battery system assembled with selected six RMs for real case consistency investigations. It is found that results from CV to galvanostatic cycling tests are consistent for halides and organometallic RMs, where the former exhibit much higher stability. However, the organic RMs show high reversibility in CV but low in battery cycling results. Density functional theory calculations are carried out to gain more understanding of the stability and redox potentials of the RMs. This study provides comparative information to select the most reliable RMs for Li-O-2 batteries along with new fundamental understanding of their electrochemical activity and stability.
Hydrothermal liquefaction (HTL) is a promising method for processing wet biomass and waste feedstock to produce biofuels. During the HTL process, proteins and other biomolecules in certain feedstock get converted into nitrogenous compounds in produced biocrude, which represents a major challenge to further upgrading them into fuels. One promising approach is to separate nitrogenous compounds from the biocrude using polymeric resins. In this study, experiments were conducted to down-select sorbent and resin systems using a nitrogen-compound-containing surrogate biocrude. We model the binding interactions between an Amberlyst polymeric resin with various compounds present in the biocrude mixture such as nitrogenous compounds like pyrrole, pyridine, hexanamide, and representative co-existing compounds like phenol and dodecanoic acid. To ascertain the efficiency of various resins in the denitrogenation process, we have developed a quantitative structure–function model for the interacting components in the mixture. Our results suggest that the Amberlyst resin is a viable candidate for efficient removal of target nitrogen-containing compounds (such as pyridine) from the biocrude as a result of favorable interactions. The computational studies provide some insight into how and why the identified resin (Amberlyst) works in selective extraction of nitrogenous compound(s).
Block copolymers (BCPs) offer distinct advantages for vat photopolymerization by enabling mechanically programmable network structures through microphase-separated morphologies that can be kinetically trapped during curing, yielding properties unattainable in homogeneous resins. However, the respective roles of repeat-unit sequence and solvent environment, together with their interplay in directing network formation and mechanical performance, remain unclear. Here, we synthesize a series of CO 2 -based polycarbonate copolymers comprising a crosslinkable glassy poly(vinyl cyclohexene carbonate) (PVCHC, A block) and a non-crosslinkable soft poly(propylene carbonate) (PPC, B block). The polymer sequence is systematically varied (ABA, BAB, and statistical), and solvent choice controls block-selective swelling to jointly control gelation behavior, microphase morphology, and mechanical response through changes in the accessibility and local environment of photocrosslinkable vinyl groups during network formation, as revealed by photorheology and small angle x-ray scattering. By tuning polymer sequence and curing solvent, we transform nominally identical formulations from brittle to highly ductile materials, achieving a three-orders-of-magnitude range in toughness (0.003 to 9.1 MJ m −3 ). These results establish clear structure–processing–property relationships and identify polymer sequence and selective solvation as powerful strategies for programming both printability and performance of block copolymer resins for additive manufacturing.
Abstract A process for the production of tens to hundreds of GBq amounts of zirconium-88 ( 88 Zr) using proton beams on yttrium was developed. For this purpose, yttrium metal targets (≈20 g) were irradiated in a ~16 to 34 MeV proton beam at a beam current of 100–200 µA at the Los Alamos Isotope Production Facility (IPF). The 88 Zr radionuclide was produced and separated from the yttrium targets using hydroxamate resin with an elution yield of 94(5)% (1σ). Liquid DCl solution in D 2 O was selected as a suitable 88 Zr sample matrix due to the high neutron transmission of deuterium compared to hydrogen and an even distribution of 88 Zr in the sample matrix. The separated 88 Zr was dissolved in DCl and 8 µL of the obtained solution was transferred to a tungsten sample can with a 1.2 mm diameter hole using a syringe and automated filling station inside a hot cell. Neutron transmission of the obtained 88 Zr sample was measured at the Device for Indirect Capture Experiments on Radionuclides (DICER).
We selected several porous materials including PNW-24, CC3, SAPO-34, SAPO-56 and PNW-6, as the basis for fabricating membranes for Kr/Xe separation. Initially, we synthesized powder samples of the candidates and confirmed their crystallinity and morphology with X-ray diffraction and microscopy. In the case of PNW-24 and PNW-6, we further confirmed its Xe selectivity through Xe and Kr adsorption experiments, while we relied on literature reports for CC3, SAPO-34 and SAPO-56. We subsequently proceeded to fabricate membranes on porous alumina supports using techniques such as seeded-assisted secondary growth, in-situ growth and solution-processed method. PXRD on the membranes verified that the structures were well-grown on the surface of alumina support, while SEM provided visual confirmation of particle morphology. Importantly, defects were not visually observed in the fabricated membranes, which was further verified with pressure retention tests. We analyzed the separation performance of the synthesized membranes using a dilute gas mixture comprising of xenon, krypton and argon. We focused on PNW-6 to optimize the synthesis reaction time and study the effects of time on gas separation. While more research is necessary to reach a comprehensive conclusion, in alignment with our milestones, we have successfully achieved our goals.
Selective proton (H + ) permeation through the atomically thin lattice of graphene and other 2D materials offers new opportunities for energy conversion/storage and novel separations. Practical applications necessitate scalable synthesis via approaches such as chemical vapor deposition (CVD) that inevitably introduce sub-nanometer defects, grain boundaries and wrinkles, and understanding their influence on H + transport and selectivity for large-area membranes is imperative but remains elusive. Using electrically driven transport of H + and potassium ions (K + ) we probe the influence of intrinsic sub-nanometer defects in monolayer CVD graphene across length-scales for the first time. At the micron scale, the areal H + conductance of CVD graphene (~4.5-6 mS cm -2 ) is comparable to that of mechanically exfoliated graphene indicating similarly high crystalline quality within a domain, albeit with K + transport (~1.7 mS cm -2 ). However, centimeter-scale Nafion|graphene|Nafion devices with several graphene domains show areal H + conductance of ~339 mS cm -2 and K + conductance of ~23.8 mS cm -2 (graphene conductance for H + is ~1735 mS cm -2 and for K + it is ~47.6 mS cm -2 ). Using a mathematical-transport-model and Nafion filled polycarbonate track etched supports, we systematically deconstruct the observed orders of magnitude increase in H + conductance for centimeter-scale CVD graphene. The mitigation of defects (>1.6 nm), wrinkles and tears via interfacial polymerization results in a conductance of ~1848 mS cm -2 for H + and ~75.3 mS cm -2 for K + (H + /K + selectivity of ~24.5) via intrinsic sub-nanometer proton selective defects in CVD graphene. We demonstrate atomically thin membranes with significantly higher ionic selectivity than state-of-the-art proton exchange membranes while maintaining comparable H + conductance. Our work provides a new framework to assess H + conductance and selectivity of large-area 2D membranes and highlights the role of intrinsic sub-nanometer proton selective defects for practical applications.
Porous carbon (PC) has been widely regarded as one of the most promising absorbents for methane storage. Studies show that its uptake capacity and selectivity highly depend on textural structures. Although much effort has been made, unveiling their detailed structure-performance relationship remains a challenge. Here, we propose an innovative study where, with the assistance of machine learning, the hidden relationship of the textural structures of PC with the methane uptake and separation can be derived from existing data in material literature. Machine learning models were trained by the data, including specific surface area, micropore volume, mesopore volume, temperature, and pressure as the input variables and methane uptake as the output variable for prediction. Among the tested models, the multilayer perceptron (MLP) shows the highest accuracy in predicting the methane uptake. In addition, the model enables to automatically construct a uptake performance map in terms of micropore volume and mesopore volume. The obtained MLP model was also extended to explore the CO 2 /CH 4 selectivity by retraining it with the data collected from literature of PC for the CO 2 uptake. Finally, the constructed 2D selectivity map shows that the high selectivity can be achieved in the low CH 4 uptake region.
Memory effect in ion transport (IT) at the solid–solution interface is uniquely attractive in that the conductance depends on or “memorizes” the previous states. Hysteretic and rectified transport properties offer exciting potential to developing advanced iontronics and neuromorphic functions, improving the efficiency of energy conversion and electrochemical processes, and overcoming the selectivity-throughput bottleneck in the enrichment of low abundant species for environment- and energy-friendly separations, among others. Herein, memory effects are discovered in the rectified electrokinetic IT through anodized aluminum oxide (AAO) membranes containing densely packed highly ordered nanochannels (10 10 per cm 2 ). Characteristic memristor responses of pinched current–potential loops are resolved in voltammetric experiments and successfully reproduced through finite element simulation. Excitatory and inhibitory conductance states are shown to arise from the enrichment and depletion of mobile charge carriers. Structurewise, the transport symmetry is broken by the barrier oxide layer (BOL) on the one end of the cylindrical nanochannels across the AAO membranes. Charge selectivity is attributed to the gradient(s) of the space charge density across the BOL characterized by depth profiling via X-ray photoelectron spectroscopy analysis. The space charge gradient(s) overcomes the fundamental limitation of widely exploited surface charge effects to enable intense rectification and hysteresis prevailing at very high ionic concentrations up to 1–2 M. A new strategy is developed for controlling the preferential IT direction and selectivity via counterion intercalation and extraction/exchange. Mechanistic understanding is further confirmed through parameter variations such as potential scan rate and ionic strength, which also demonstrates convenient controls of the related functions.
Glassy 6FDA-based polyimides are attractive membrane materials for many industrially important gas separations; however, plasticization in aggressive natural gas often causes significant loss in CO 2 /CH 4 selectivity. In this study, a family of thermally cross-linkable 6FDA-based polyimides containing carboxyl groups were synthesized and cross-linked as dense films via decarboxylation-induced thermal crosslinking. As well as chemical structure, crosslinking temperatures above and below T g are shown to be synergistic tools. Our results demonstrate that structure evolution during the decarboxylation-induced crosslinking process is affected significantly by the 3,5-diaminobenzoic acid (DABA) content in the polymer backbone. Even for a 50/50 CO 2 /CH 4 binary mixture with feed pressure up to 800 psia, decarboxylation-induced crosslinking provides attractive gas separation performance and plasticization resistance. Combined facile structure tunability, crosslinkability and high asymmetric fiber spinnability make the cross-linkable 6FDA-based polyimides a versatile platform for diverse aggressive natural gas feeds encountered in practice. Finally, our study provides insights into material design of thermally cross-linkable polymer membranes for such a broad spectrum of aggressive gas separations.
Greater selectivity and controls in the ion transport dynamics are essential in fields such as charge storage, separation, energy storage and conversion, neuromorphic computing and learning, electrochemistry, to name a few. Mechanistic insights into the intriguing hysteresis effects in the rectified electrokinetic transport through single conical nanopipettes are unveiled by combining time-resolved electroanalytical experiments with numeric simulation. Cations as counterions for surface charges are found to dominate not just the through-nanopore flux but also the hysteresis charges, that is, the net enriched or expelled charges during the transport process. Built on our earlier report on the through-nanopore ion flux dominated by counterions for surface charges, the “trapped ions” or hysteresis charges are analyzed herein. Cation selectivity is almost 100% in the hysteresis charges during the potential scans in low conductivity states driven by the combined applied and intrinsic surface electrical fields. Surprisingly, the cation selectivity in the total hysteresis charges remains high at 70–80% over a wide bulk concentration range in the high conductivity (HC) states, where higher ionic strength due to ion enrichment would decrease electrostatistic effects and thus ion selectivity. The retained high selectivity at HC is explained by the competition effects of electroosmotic flow against the co-ion migration. Furthermore, the respective cation and anion portions in the total hysteresis charges over a wide range of ionic strength and measurement conditions provide generalizable strategies for improvements in both transport throughput and selectivity.
Abstract Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol‐gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource‐H 2 separation processes.
Metal organic framework (MOF)-based mixedmatrix membranes (MMMs), which embed MOF particles in polymer matrices, combine the advantages of polymeric and inorganic membranes. Multiple previous studies have used the Maxwell model together with molecular simulations and machine learning (ML) to predict the performance of MOF/polymer MMMs. However, the assumption of rigid MOF frameworks in molecular simulations limited the accuracy of the data used in the predictions, particularly in predicting molecular diffusivities. We developed a novel workflow integrating ML models with consideration of MOF flexibility to predict the permeability and selectivity of 131,722 MMMs for CO 2 /CH 4 , O 2 /N 2 and He/H 2 separations. The full range of achievable MMM performance within the Maxwell model was analyzed, and several promising MOFs were identified using this workflow. This approach offers an efficient tool for screening any polymer and MOF combination in gas separation applications.
The Dark Energy Spectroscopic Instrument (DESI) will execute a nearly magnitude-limited survey of low redshift galaxies (0.05 ≤ z ≤ 0.4, median z ≈ 0.2). Clustering analyses of this Bright Galaxy Survey (BGS) will yield the most precise measurements to date of baryon acoustic oscillations and redshift-space distortions at low redshift. DESI BGS will comprise two target classes: (i) BRIGHT (r < 19.5 mag), and (ii) FAINT (19.5 < r < 20 mag). Here we present a summary of the star-galaxy separation, and different photometric and geometrical masks, used in BGS to reduce the number of spurious targets. The selection results in a total density of ~800 objects deg -2 for the BRIGHT and ~600 objects deg -2 for the FAINT selections. A full characterization of the BGS selection can be found in Ruiz-Macias et al.
Abstract Molecular sieving may occur when two molecules compete for a nanopore. In nearly all known examples, the nanopore is larger than the molecule that selectively enters the pore. Here, we experimentally demonstrate the ability of single-wall carbon nanotubes with a van der Waals pore size of 0.42 nm to separate n-hexane from cyclohexane—despite the fact that both molecules have kinetic diameters larger than the rigid nanopore. This unexpected finding challenges our current understanding of nanopore selectivity and how molecules may enter a tight channel. Ab initio molecular dynamics simulations reveal that n-hexane molecules stretch by nearly 11.2% inside the nanotube pore. Although at a relatively low probability (28.5% overall), the stretched state of n-hexane does exist in the bulk solution, allowing the molecule to enter the tight pore even at room temperature. These insights open up opportunities to engineer nanopore selectivity based on the molecular degrees of freedom.
Stable isotope ratio measurements of carbon atoms using isotope ratio mass spectrometry (IRMS) can be an effective tool for quantifying biogenic carbon in co-processed fuels, with results approaching the precision and accuracy of accelerator mass spectrometry (AMS). The lower cost of an IRMS may enable deployment to refineries, improving access and analysis turnaround times (≤2 hours), and, by extension, provide data that can allow process optimization to maximize renewable carbon in desired refinery products. This project explored the integration of chemical separation with IRMS analyses to enable highly detailed tracking of biogenic carbon into fuel product streams separated by boiling point range, chemical class, or specific compound. Forty-nine fuels and fuel components of fossil and biogenic origin, spanning gasoline and diesel boiling point ranges, were received from three refiners and were analyzed for their δ 13 C values via IRMS. Results spanned a 13 C range from ca. 10‰ to 44‰ and reflect materials derived from sustainable sources (e.g., C4 or C3 plants, animal-based pathways, syngas) or from fossil-derived fuels. Common ranges are approximately 18‰ to 9‰ and approximately 30‰ to 20‰ for C4 and C3 plants, respectively, and approximately 34‰ to 24‰ and approximately 70‰ to 33‰ for petroleum-derived fuels and methane, respectively. Fuel-like standards were developed and tested using direct-injection elemental analyzer (EA) IRMS for liquid fuels. This method was compared with the published methods, yielding statistically similar results. Four blend curve sets were produced ranging from 0% to 100% of a fuel containing biogenic carbon, focusing on 0% to 10% biogenic carbon. Linear fits were the most applicable for two of the four blend curve sets; however, two sets were found to exhibit slightly quadratic behavior, which was more pronounced in low biogenic blend samples, necessitating second-order fits. The origin of the slight quadratic behavior remains unclear; however, the discussion points to possible interpretations. CanmetENERGY thoroughly characterized a majority of the samples using one- and two-dimensional gas chromatography (GC and GC×GC, respectively) and other analyses. Selected samples were subjected to solid phase extraction (SPE) for saturate, olefin, aromatic, and polar (SOAP) analysis, and the resulting solvent-diluted fractions containing saturates and aromatics were returned to Pacific Northwest National Laboratory (PNNL), where the solvent was removed via evaporation or physical separation using GC techniques. Characterization and separations provided an understanding of saturate and aromatic content, as well as boiling point ranges for each sample and sample fraction. Samples resulting from SPE were examined using EA-IRMS and gas chromatography combustion IRMS (GC-C-IRMS) analyses. Both approaches suggest that the range in values between end-members can be increased by selecting the paraffinic or aromatic fraction of the end-member or by selecting among individual compounds resulting from GC separation of the paraffinic fractions. Considerable work remains to put these approaches into practice and statistically validate the benefit for using a fraction or individual compound over bulk analysis of a sample. However, initial results suggest that separations provide advantages for samples having blend ratios of less than 10% biogenic blendstocks. 13 C results showed statistically similar biofuel blend results to those obtained at PNNL, although additional work is needed to obtain better reproducibility. Select samples were sent to Los Alamos National Laboratory (LANL) for IRMS measurements and Beta Analytics for AMS measurements. This work suggests that IRMS and AMS yield closely comparable results and in some circumstances, IRMS could serve as a surrogate for AMS. While additional work is needed to better resolve statistical advantages for separations and better show the comparable nature of IRMS and AMS in both the biogenic carbon analysis of bulk chemical classes, initial results from this study suggest that these should be pursued in order to proliferate this approach for quantifying biogenic carbon in transportation fuels to the refinery level, thereby potentially enabling process optimization in co-processing scenarios.
Two-dimensional (2D) materials bring a great opportunity to fabricate molecular sieving membranes that can potentially break the permeability-selectivity trade-off. Although 2D laminar membranes with interlayer nanochannels as molecular sieving channel were widely studied, for most of reported 2D laminar membranes, it is of a great challenge to fabricate highly ordered interlayer nanochannels for mass transport. Herein, we report a novel kind of black phosphorene membrane which is made from the stacking of highly ordered 2D black phosphorene nanoflakes. The as prepared black phosphorene membrane shows H 2 permeance > 1000 GPU and H 2 /CO 2 selectivity > 100 for H 2 /CO 2 mixed gas, demonstrating an extremely high gas separation performance. The DFT calculation results demonstrate that the interlayer galleries in the black phosphorene membrane allow the H 2 passing through easily while block the other gases with bigger kinetic diameters, matching well with the experimental findings. In conclusion, the present results indicate that the interlayer galleries in the black phosphorene membrane can be applied as molecular sieving channels for gas separation.