Life support system for space flights of extended time periods - Liquid/gas separation mechanisms
Life support system for extended space flights - liquid-gas separation mechanisms
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Life support system for extended space flights - liquid-gas separation mechanisms
To meet performance requirements, the next generation of gas separation membranes will need both high gas permeability and selectivity, attainable if we could coax adsorbates to minimize random Brownian motion and produce direction-specific diffusion along a desired axis. In this atomistic modeling study, we detail how direction-specific diffusion of CO 2 can be achieved in chiral hexagonal boron nitride nanotubes (hBNNTs) by means of a non-Knudsen diffusion mechanism. Our findings detail how this mechanism of diffusion is driven by interactions with the tube walls and enables the CO 2 molecules to diffuse along the nanotube’s z-axis with minimized collisions and directional changes. hBNNTs with chiral indices exhibit CO 2 diffusion rates faster than non-chiral tubes of comparable and larger diameters. Of the hBNNTs studied, a (7,3) tube appears to be ideally sized (3.7 Å radius) exhibiting CO 2 diffusion that is 3.4 times faster than diatomic N 2 . Applying this mechanism of diffusion to hypothetical sheet membranes prepared with aligned chiral (7,3) hBNNTs results in membranes with a calculated CO 2 /N 2 permselectivity of 170 and a CO 2 permeability limit of nearly 1.35 ×10 7 Barrer, readily surpassing the Robeson upper bound for CO 2 /N 2 separations.
Metal organic frameworks (MOF) were created for the capture of noble gases (NG). They were tested to see which would be the most efficient and selective. MOFs are synthetic materials that are used in a variety of purposes: gas separations, catalysis reactions, drug delivery, and gas storage. In a previous study, there was an extremely long retention time of NG within the Ca-MOF material. Between 30-65 % of the NG was never recovered even under vacuum and at 150 °C. An understanding of this retention at a fundamental level is needed for utilizing the MOF material in industry or other applications
Cyclones are one of the most common types of gas-solid separators used in circulating fluidized bed boilers. However, cyclones typically do not allow ash to leave the system through the cyclone exit, causing ash to build up in the fluidized bed and necessitating additional systems to remove ash that builds up in the bed. In this study, an alternative “disengager” gas-solid separator is proposed as a way of inherently separating small and large solids, resulting in a gas-solid-solid separation system where ash is allowed to leave the system along with gas while the desired fluidized bed material is retained. Unlike cyclones, which rely on centrifugal force to separate solids and gas, the disengager separates based on entrainment velocity of the particles. Upwards-flowing gas and particles strike a deflection plate and enter the disengaging chamber where particles with low terminal velocity such as ash fines flow with the gas, while larger particles such as sand fall to the bottom of the separator and are returned to the fluidized bed. In this study, several different proposed disengager configurations are simulated and compared to a typical cyclone using computational fluid dynamic (CFD) simulations. Furthermore, it was found that separation efficiency in the disengager is strongly influenced by the size of the deflection plate, rather than by the size of the unit itself. The predicted separation efficiency showed that compared to a cyclone, the disengager design allows significantly more ash to exit the system but retains a similar amount of desirable material. Additionally, the disengager was predicted to not suffer significantly more erosion that a cyclone.
The project was to perform testing that establishes a baseline of precombustion carbon capture performance when combined with coal- and biomass-derived syngas. Goals of the project were to generate syngas from a matrix of coal types, biomass types, and varied fuel concentrations. Solvent performance and contaminant accumulation within the acid gas separation system (AGSS) were examined.
A series of self-semi-interpenetrating network (ssIPN) thin films based on PIM-1 structure were developed by end-cross-linking telechelic PIM-1 oligomers end-capped with curable carboxylic acid groups to form model networks, which are penetrated by linear high-molecular-weight PIM-1 chains. ssIPN films with systematically varied network content ranging from 10 to 30 wt % were comprehensively examined on their microstructure and gas permeation properties. Fresh PIM-1 ssIPN films exhibited gas separation performances close to those of as-cast linear PIM-1, where the films closely followed the upper bound trade-off line, gaining as much selectivity as they lose gas permeability as the network content increases. This indicates that gas permeability is largely preserved despite cross-linking. Wide-angle X-ray scattering supported this observation, with peaks shifting toward lower d-spacing as oligomer content increased, suggesting tighter chain packing with higher cross-linkable oligomer loading. In physical aging studies over two months, all ssIPN films outperform linear PIM-1 for H 2 /CH 4 and O 2 /N 2 separations. Notably, the PIM-1 ssIPN with 10 wt % network content showed the best physical aging resistance, with negligible permeability loss even after one month. Finally, these findings highlight a promising macromolecular strategy for enhancing the physical aging resistance of microporous polymer membranes for gas separation.
Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF 3 ) 2 Bp]Cu} 3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF 3 ) 2 Bp]Cu(C 2 H 4 ). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C 2 H 4 /C 2 H 6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a “live” picture of the reversible conversion between [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C 2 H 4 . As a result, molecular structures of trinuclear {[(CF 3 ) 2 Bp]Cu} 3 and mononuclear [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) are also presented.
Oral presentation for ACS Spring Meeting
Carbon molecular sieve (CMS) membranes are attractive candidates to meet requirements for challenging gas separations. The added ability to maintain such intrinsic properties in an asymmetric morphology with a structure that we term a “Pseudo Wheel+Hub & Spoke” asymmetric form offers new opportunities. For CMS membrane, specifically, the structure provides both selective layer support and low flow resistance even for high feed pressures and fluxes in CO 2 removal from natural gas. Further, this capability is unavailable to even rigid glassy polymers due to the much higher modulus of CMS materials. Combining precursor asymmetric hollow fiber formation and optimized pyrolysis creates a defect free CMS proof-of-concept membrane for this application. Facile formation of the sheath-core spun precursor with a 6FDA-DAM sheath and Matrimid® core also avoids the need to seal defects before or after the carbonization of the precursors. The composite CMS membrane shows CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 64.3 and CO 2 permeance of 232 GPU at 35 °C. A key additional benefit of the approach is reduction in use of the more costly high performance 6FDA-DAM in a composite sheath-core CMS membrane with the “Pseudo Wheel+Hub & Spoke” structure.
Gas-separation membranes are a critical industrial component for a low-carbon and energy-efficient future. As a result, many researchers have been testing membrane materials over the past several decades. Unfortunately, almost all membrane-based testing systems are home-built, and there are no widely accepted material standards or testing protocols in the literature, making it challenging to accurately compare experimental results. Further, in this multi-lab study, ten independent laboratories collected high-pressure pure-gas permeation data for H 2 , O 2 , CH 4 , and N 2 in commercial polysulfone (PSf) films. Equipment information, testing procedures, and permeation data from all labs were collected to provide (1) accepted H 2 , O 2 , CH 4 , and N 2 permeability values at 35°C in PSf as a reference standard, (2) statistical analysis of lab-to-lab uncertainties in evaluating permeability, and (3) a list of best practices for sample preparation, equipment set-up, and permeation testing using constant-volume variable-pressure apparatuses. Results summarized in this work provide a reference standard and recommended testing protocols for pure-gas testing of membrane materials.
KIER and NETL will collaborate to study hydrate-based technologies to enhance desalination, gas separation, and hydrocarbon flow through pipelines and wellbores. With optimized selections of hydrate formers and reactors, gas hydrates can be effective and economic mechanisms of separation for solid-water and gas mixtures, and gas hydrate formation or dissociation can be significantly delayed or expedited with suitably selected additives. Comprehensive laboratory studies, including identifying novel hydrate formers or inhibitors to control temperature and pressure requirements and understanding their working mechanism or developing reactor systems for production of large quantities of hydrates, will be performed at both KIER and NETL either parallelly or serially.
KIER and NETL will collaborate to study hydrate-based technologies to enhance desalination, gas separation, and hydrocarbon flow through pipelines and wellbores. With optimized selections of hydrate formers and reactors, gas hydrates can be effective and economic mechanisms of separation for solid-water and gas mixtures, and gas hydrate formation or dissociation can be significantly delayed or expedited with suitably selected additives. Comprehensive laboratory studies, including identifying novel hydrate formers or inhibitors to control temperature and pressure requirements and understanding their working mechanism or developing reactor systems for production of large quantities of hydrates, will be performed at both KIER and NETL either parallelly or serially.
Metal–organic frameworks (MOFs) have premium exceptional properties for a variety of functions, such as gas separation and storage and catalysis. The large variety of possible inorganometallic nodes and organic linkers provide an almost unlimited number of combinations for assembling MOFs, which makes the experimental characterization and examination of all potentially useful combinations practically impossible. Furthermore, experimental studies of MOFs typically fall short in uncovering crucial details regarding their mechanisms of action or the molecular details responsible for their functional properties, such as the nature of adsorbate binding or the structures of transition states. Computational modeling has, therefore, become an efficient and important tool for strategizing the functionalization of MOFs and explicating the mechanisms of their functions. Furthermore, we review the computational methodologies used for computational studies of MOFs, especially Kohn–Sham density functional theory and combined quantum mechanical and molecular mechanical methods for calculating their structural, electronic, and magnetic properties, as well as for understanding the mechanisms of MOFs' applications to magetic devices, thermal conduction, gas adsorption, separation, storage, and sensing, thermal catalysis, photocatalysis, and electrocatalysis.
In designing membrane systems, the synergy between membrane materials and the process design is often overlooked. In this paper, we present a mixed-integer nonlinear programming (MINLP) model for synthesizing membrane systems while simultaneously designing the respective membrane materials for multicomponent gas separation. The approach considers superstructure representations for systems with: (1) same, (2) potentially different, and (3) property-targeting membrane materials. In the first two systems, the selection of membrane material is a decision, while in the final type, membrane permeances are subject to optimization. Physics-based surrogate models are used to describe permeation in crossflow and countercurrent flow permeators. We show that, through a case study of biogas upgrading, our approach obtains high quality solutions. Furthermore, we use the proposed approach while considering permeance-based production cost to find the optimal membrane.
NASA has performed physical science microgravity flight experiments in the areas of combustion science, fluid physics, material science and fundamental physics research on the International Space Station (ISS) since 2001. The orbital conditions on the ISS provide an environment where gravity driven phenomena, such as buoyant convection, are nearly negligible. Gravity strongly affects fluid behavior by creating forces that drive motion, shape phase boundaries and compress gases. The need for a better understanding of fluid physics has created a vigorous, multidisciplinary research community whose ongoing vitality is marked by the continuous emergence of new fields in both basic and applied science. In particular, the low-gravity environment offers a unique opportunity for the study of fluid physics and transport phenomena that are very relevant to management of fluid - gas separations in fuel cell and electrolysis systems. Experiments conducted in space have yielded rich results. These results provided valuable insights into fundamental fluid and gas phase behavior that apply to space environments and could not be observed in Earth-based labs. As an example, recent capillary flow results have discovered both an unexpected sensitivity to symmetric geometries associated with fluid container shape, and identified key regime maps for design of corner or wedge-shaped passive gas-liquid phase separators. In this presentation we will also briefly review some of physical science related to flight experiments, such as boiling, that have applicability to electrochemical systems, along with ground-based (drop tower, low gravity aircraft) microgravity electrochemical research. These same buoyancy and interfacial phenomena effects will apply to electrochemical power and energy storage systems that perform two-phase separation, such as water-oxygen separation in life support electrolysis, and primary space power generation devices such as passive primary fuel cell.
An effective cross-linking technique allows a viscous, highly gas permeable hydrophilic polyphosphazene to be cast as solid membrane films. By judicious blending with other polyphosphazenes to improve mechanical properties, a membrane exhibiting the highest CO2 permeability (610 barrer) combined with good CO2/N2 selectivity (35) among polyphosphazenes is described here. The material demonstrates performance stability after 500 hours of exposure to a coal-fired power plant flue gas, making it attractive for use in carbon capture applications. Its CO2/N2 selectivity under conditions up to full humidity is also stable, and although the gas permeability does decline, the performance is fully recovered upon drying. The high molecular weight of these heteropolymers also allows them to be cast as a thin selective layer on an asymmetric porous membrane, yielding CO2 permeance of 1200 GPU, CO2/N2 pure gas selectivity of 31, which does not decline over 2000 hours due to physical aging. In addition to gas separation membranes, this cross-linked polyphosphazene can potentially be extended to other applications such as drug delivery or proton exchange membranes which take advantage of the polyphosphazene’s versatile chemistry.
Pore space partition (PSP) concept is a synthetic design concept and can also serve as a structure analysis method useful for next-step synthetic planning and execution. PSP provides an integrated chemistry-topology-focused tool to design new materials platforms. While PSP is no less effective for making large-pore materials, the growing importance of small-molecule gas storage and separation for green-energy applications provides impetus for developing small-pore materials for which the PSP strategy is uniquely suited. Currently, the best embodiment of the PSP concept is the partitioned-acs (pacs) platform in which both fine or coarse adjustments to the building blocks have sparked a transformation of a prototype framework into a huge and continuously expanding family of chemically robust materials with controllable pore metrics and functionalities suitable for tailored applications. The pacs compositional diversity results from the platform’s intrinsic multi-module nature, geometric flexibility and tolerance towards individual module variations, and mutual structure-directing effects among various modules, all of which combine to enable the molecular-level uniform co-assemblies of chemical components rarely seen together elsewhere. Here, in this contribution, we present an overview of different pore space engineering methods and how different MOF materials have contributed to important advances in chemical stability, industrial gas storage and gas separation. In particular, we will focus on synthetic assembly of the pacs system, highlighting the differences of pacs materials from other MOF platforms and advantages of pacs materials in enhancing various MOF properties.