Results for “adsorption process” — Page 13

NASA NTRS2004

Chlorine stable isotopes in sedimentary systems: does size matter?

Stable isotope abundances vary because of size differences. The chlorine stable isotope system was one of the first described theoretically, but had a slow, disappointment strewn development, relative to other elements. Method improvement gave only small, but significant, differences in compositions of geological materials. Eventually, brines and groundwater chlorides gave larger differences. Physical processes like diffusion and adsorption, probably are the main controls of groundwater compositions. Recent work on anthropogenic groundwater contaminants shows variations resulting from manufacturing processes; implying possibilities of tracing sources.

chlorine stable isotopes↗

NASA NTRSDate not supplied

Modeling Evolvable Water Recovery Systems for Short and Long-Duration Missions in Partial Gravity

Water recovery technologies on the International Space Station (ISS) are designed and optimized for microgravity environments, thus creating a need for innovative systems optimized for mission operations in the presence of gravity. Alternative water recovery technologies under research by the Life Support Systems division were compiled into a series of Partial Gravity Water Recovery System (PGWRS) architectures. Individual unit processes were modeled via fundamental physical-chemical process equations to simulate their method of treatment, including chemical or biological oxidation, flash evaporation, filtration, or a combination of adsorption and ion exchange processes. Dimension and sizing data were then utilized to scale each architecture. Modeling was completed on an assortment of architectures assuming three scenarios in which treatment methods could take advantage of partial gravity: a short-duration mission with a temporary surface habitat, a longer duration mission with a more permanent habitat, and a long duration mission without resupply. Total system mass was estimated to quantitatively compare architectures within scenarios, but qualitative observations were also made regarding system robustness, flexibility, and capacity to meet more stringent demands. Technologies that traded most favorably between the scenarios were those that included a pre-oxidation stage to minimize mass loading to downstream absorption and ion exchange beds, exploited gravity in liquid-vapor separation processes, and reconstituted wastewater components into recyclable material streams.

Avery Carlson↗

NASA NTRSDate not supplied

Modeling Evolvable Water Recovery Systems for Short and Long-Duration Missions in Partial Gravity

Water recovery technologies on the International Space Station (ISS) are designed and optimized for microgravity environments, thus creating a need for innovative systems optimized for mission operations in the presence of gravity. Alternative water recovery technologies under research by the Life Support Systems division were compiled into a series of Partial Gravity Water Recovery System (PGWRS) architectures. Individual unit processes were modeled via fundamental physical-chemical process equations to simulate their method of treatment, including chemical or biological oxidation, flash evaporation, filtration, or a combination of adsorption and ion exchange processes. Dimension and sizing data were then utilized to scale each architecture. Modeling was completed on an assortment of architectures assuming three scenarios in which treatment methods could take advantage of partial gravity: a short-duration mission with a temporary surface habitat, a longer duration mission with a more permanent habitat, and a long duration mission without resupply. Total system mass was estimated to quantitatively compare architectures within scenarios, but qualitative observations were also made regarding system robustness, flexibility, and capacity to meet more stringent demands. Technologies that traded most favorably between the scenarios were those that included a pre-oxidation stage to minimize mass loading to downstream absorption and ion exchange beds, exploited gravity in liquid-vapor separation processes, and reconstituted wastewater components into recyclable material streams.

Avery L. Carlson↗

DOE OSTI2020

Kinetics of the functionalization of mesoporous silica nanoparticles: Implications on surface group distributions, adsorption and catalysis

The post-synthesis functionalization (grafting) kinetics of mesoporous silica nanoparticles (MSN) with organotrimethoxysilanes (R-TMS) is studied via solution 1 H NMR spectroscopy. The process involves a rapid adsorption/ desorption pre-equilibrium followed by reaction of R-TMS with surface silanols. Grafting rates are affected by the functional group in R-TMS. For example, the grafting rate of aminopropyl-trimethoxysilane (AP-TMS) is one order of magnitude higher than other R-TMS. High concentrations of AP-TMS result in substrate-inhibition kinetics, likely due to steric and mobility constraints for reactant alignment at high coverage. The higher rates of AP-TMS grafting indicate a catalytic effect of amine groups. This effect depends on the amine’s basicity and can be used to control the grafting rates and degree of condensation of other R-TMS. Adjusting the rate of mercaptopropyl-trimethoxysilane (MP-TMS) grafting using amines gives MP-MSN materials of varying adsorptive and catalytic activities, illustrated by Pd scavenging experiments and use of Pd@MP-MSN as catalysts for a Suzuki-Miyaura cross-coupling reaction.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Real-time observation of the exchange process between H 2 O and NO in the metal–organic framework Ni-MOF-74

Molecular exchange is a common step occurring in many technological processes such as competitive adsorption, chemical separation, capture, delivery, and release. However, the underlying principle is not fully understood, especially in nanoconfined environments where the energetics and kinetics of such processes can deviate from that on flat surfaces. In this study, we unravel the mechanism of a molecular exchange process by studying the displacement of NO by H 2 O in Ni-MOF-74 in real-time using in situ infrared spectroscopy combined with ab initio calculations. We show that weakly bound H 2 O gradually displaces strongly bound NO on the metal sites by first weakening the M–N bond through forming H-bond and then moving the NO away so that it eventually desorbs. Interestingly, we further find that additional water facilitates this exchange by significantly lowering the kinetic barrier associated with this process as well as the overall energy of the final state. Although our study focuses on Ni-MOF-74, we believe that our finding and explanation of unexpected exchange phenomena—where strongly adsorbed molecules are apparently easily displaced by much weaker bound H 2 O—is applicable to a much larger group of frameworks and will be helpful in designing and improving MOFs for real-world applications where humidity is often present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1964

Some Theoretical Aspect of Cryosorption

When a gas or vapor is allowed to come to equilibrium with a solid surface, the concentration of gas molecules is always found to be greater in the immediate vicinity of the surface than in the free gas phase, regardless of the nature of the gas or of the surface. The process by which this surface excess is formed is termed adsorption. In any solid, the atoms at the surface are subject to unbalanced forces of attraction normal to the surface plane; the balance of forces is partially restored by the adsorption of gas molecules. If the forces responsible for adsorption are of van der Waals type, the process is called physical adsorption. Furthermore, if the solid (and its surface) are maintained at relatively low temperatures (say 50°K or below), the term cryosorption is used.

ADSORPTION↗

DOE OSTI2020

Novel Application of Hybrid Anion Exchange Resin for Phosphate Desorption Kinetics in Soils: Minimizing Re-Adsorption of Desorbed Ions

The process of phosphate desorption from soils is difficult to measure using stirred batch techniques because of the accumulation of desorbed ions in a bathing solution. To accurately measure the apparent rate coefficient of phosphate desorption from soils, it is necessary to remove the desorbed ions. In this study, a novel hybrid (i.e., iron oxide coated) anion exchange resin was used as a sink to study long-term (seven days) P desorption kinetics in intensively managed agricultural soils in the Midwestern U.S. (total phosphorus (TP): 196–419 mg/kg). The phosphate desorption kinetics in the hybrid anion exchange resin method were compared with those in the other conventional batch desorption method with pure anion exchange resins or without any sink. The extent of P desorption in the hybrid resin methods was >50% of total desorbed phosphate in the other methods. The initial kinetic rate estimated in the pseudo-second-order kinetic model was also highest (3.03–31.35 mg/(g·hr)) in the hybrid resin method when the same soil system was compared. This is because adsorbed P in the hybrid resins was nearly irreversible. The hybrid anion exchange resin might be a new and ideal sink in measuring the P desorption process in soils and sediments

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Analyses of hot/warm CO2 removal processes for IGCC power plants

Abstract Compared with a pulverized coal power plant, the integrated gasification combined cycle (IGCC) has several advantages, including, among others better environmental performance and low CO 2 capture cost. Hot/warm CO 2 removal from syngas has also been a subject of research due to its potentially higher thermal efficiency. In this study, we proposed a generic adsorption based hot/warm CO 2 removal process for IGCC power plants. Through analyses of the proposed generic process we have demonstrated that higher temperature of the hot/warm CO 2 removal process will results in larger heat of adsorption, which in turns may increase energy consumption of the process. Under most of the operating temperature range, hot/warm CO 2 removal process will lead to more electricity loss compared to the baseline Selexol process. However, if the adsorption step takes place at a temperature close to or higher than the highest steam temperature in steam cycle, our analysis indicates that the process may lead to minimal electricity loss. The study also provided some other insights into the pathways for hot/warm CO 2 removal process to improve its energy performance through process and sorbent designs. Graphical Abstract

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Energetics of CO 2 and H 2 O adsorption on alkaline earth metal doped TiO 2

The process of CO 2 and H 2 O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO 2 and H 2 O adsorption on TiO 2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO 2 surface affinity to CO 2 and H 2 O, TiO 2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO 2 nanoparticles, both CO 2 and subsequent H2O adsorption amounts could be increased. CO 2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2014

Black Molecular Adsorber Coatings for Spaceflight Applications

The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

adsorption↗

NASA NTRS2014

Black Molecular Adsorber Coatings for Spaceflight Applications

The molecular adsorber coating is a new technology that was developed to mitigate the risk of on-orbit molecular contamination on spaceflight missions. The application of this coating would be ideal near highly sensitive, interior surfaces and instruments that are negatively impacted by outgassed molecules from materials, such as plastics, adhesives, lubricants, epoxies, and other similar compounds. This current, sprayable paint technology is comprised of inorganic white materials made from highly porous zeolite. In addition to good adhesion performance, thermal stability, and adsorptive capability, the molecular adsorber coating offers favorable thermal control characteristics. However, low reflectivity properties, which are typically offered by black thermal control coatings, are desired for some spaceflight applications. For example, black coatings are used on interior surfaces, in particular, on instrument baffles for optical stray light control. Similarly, they are also used within light paths between optical systems, such as telescopes, to absorb light. Recent efforts have been made to transform the white molecular adsorber coating into a black coating with similar adsorptive properties. This result is achieved by optimizing the current formulation with black pigments, while still maintaining its adsorption capability for outgassing control. Different binder to pigment ratios, coating thicknesses, and spray application techniques were explored to develop a black version of the molecular adsorber coating. During the development process, coating performance and adsorption characteristics were studied. The preliminary work performed on black molecular adsorber coatings thus far is very promising. Continued development and testing is necessary for its use on future contamination sensitive spaceflight missions.

adsorption↗

NASA NTRSDate not supplied

Design of an Adsorption Bed for Exploration Trace Contaminant Control

The state-of-the-art in long mission duration spacecraft trace contaminant control processes relies on physical and chemical adsorption for contaminant removal. Target species for adsorption include low and semivolatile organic compounds while chemisorption is utilized for metabolic ammonia control. When adsorption is employed in conjunction with a high temperature oxidation process, a complementary impact on cabin air quality may be realized. The adsorption bed also serves to guard the downstream oxidation catalyst from foulants and potential poisons which may decrease its lifetime and activity. To this end, a packed adsorption guard-bed was sized to control a statistical contaminant load model over a simulated Mars transit mission duration. The updated load model incorporates flight air-quality data and contemporary metabolic source emission literature. The guard-bed was operated in tandem with an exploration prototype thermal catalytic oxidizer. The exploration guard-bed prototype included design considerations from recent flight technology demonstrations and changes intended to improve compatibility with enriched oxygen exploration cabin environments as compared to the prior-art of contaminant control system design.

Trace Contaminant Control↗

DOE OSTI2020

Separation characteristics of cations and natural organic matter in electrodialysis

Natural organic matter (NOM) in water can cause the formation of disinfection byproducts (DBPs) when NOM reacts with a disinfectant such as chlorine. Nanofiltration (NF) and reverse osmosis (RO) are effective treatment methods to remove NOM. However, the simultaneous presence of both NOM and divalent cations such as Ca 2+ can enhance fouling in NF and RO. Therefore, an appropriate pretreatment to remove such cations before NF or RO would delay fouling and perhaps improve water recovery and NOM removal efficiency. Electrodialysis (ED) is potentially an excellent pretreatment method because it separates inorganic ions well using ion exchange membranes (IEMs) but does not separate NOM well because of its size and consequent low diffusivity. This research focused on ion and NOM separation with ED using three different types of commercially available IEM pairs, two different commercially available NOM sources, and six different influents at 500 mg/L total dissolved solids in the presence or absence of both hardness (Ca 2+ and Mg 2+ ) and NOM. The target waters of interest in this research were drinking water supplies that require little or no desalination but substantial removal of NOM; after NOM separation in NF or RO, some or all of the ED concentrate can be added to the NF/RO permeate to create the finished water prior to disinfection. The results indicate that ED can effectively separate alkaline earth metal ions without separation of NOM. Cation exchange membranes with high exchange capacity, high selectivity for divalent cations are desirable, and both anion and cation exchange membranes should have low affinity for organic adsorption. As a result, the process would work particularly well for NOM with relatively low hydrophobicity, since NOM adsorption to most surfaces increases with hydrophobicity.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Low Regeneration Temperature Sorbents for Direct Air Capture of CO 2

Susteon Inc., in partnership with University of Wyoming and SoCalGas, successfully met all major technical objectives to (1) scale up the ionic liquid catalyst for amine-based sorbents for improved desorption and absorption kinetics, (2) evaluate the catalyzed amine-based sorbents for direct CO 2 capture process to determine CO 2 adsorption and desorption rates and energy requirements, and (3) based on the experimental results, develop a conceptual process design to perform a preliminary economic assessment to evaluate the potential for DAC process cost reduction using the catalyzed sorbents. Amine doped solid sorbents are effective for DAC applications and can be regenerated by heat or by a combination of heat, steam, and vacuum. The best sorbent composition identified was polyethyleneimine (PEI) on fumed silica with 200 ppm ionic liquid catalyst. This sorbent formulation was shown to have a CO 2 breakthrough capacity twice that of the non-catalyzed sorbent, in laboratory tests with air at 75% relative humidity (RH). The CO 2 adsorption rate was also 40% higher than that of the non-catalyzed sorbent. This type of sorbents has the attributes required for lowering the overall cost of DAC with high CO 2 capacity and high rate of adsorption. The combination of an industrially utilized amine-based sorbent with a highly active catalyst to form a new class of materials for DAC provides a technically viable pathway for reducing the cost of DAC to <$100/tonne of CO 2 . Laboratory measurements show that the silica/PEI (polyethyleneimine) sorbents with 100 ppm of ionic liquid catalyst have almost 100% higher CO 2 cyclic capacity and 40% higher adsorption rate. Generally, CO 2 desorption occurred at higher temperatures with a rate of desorption 10 times faster than adsorption (which occurred at ambient conditions). Therefore, adsorption rate is a much more important factor in the cost of DAC because it is directly linked to the CAPEX of the total system and the cycle time (i.e., sorbent productivity in ton/day of CO 2 captured per unit volume of the air contactor). An initial process design, coupled with techno-economic analysis, based on optimal experimental results and preliminary resulting from structured sorbent testing, showed a path to lower the DAC cost from the current cost of over $200/tonne CO 2 to less than $100/tonne with a scale-up, mature state of the technology, with projected material and process improvements. These results demonstrate the effectiveness of the catalyst in silica/PEI sorbents in enhancing sorbents’ CO 2 working capacity, in (a) increasing the rate of adsorption and desorption, and (b) in lowering the CAPEX and OPEX of the DAC system employing the ionic liquid catalyzed sorbents.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2021

Cooperative Research and Development Agreement between National Energy Technology Laboratory and Electric Power Research Institute (EPRI) [Abstract]

Carbon dioxide (CO 2 ) capture from flue gas generated by fossil fuel-fired power plants has been proposed as an efficient approach to limit CO 2 emissions to the atmosphere. Due to the high cyclic CO 2 sorption capacity, well-tuned adsorption chemistry and non-volatility, solid sorbents are widely studied for CO 2 capture processes such as pressure swing adsorption (PSA) and temperature swing adsorption (TSA). Realistic applications of traditional solid sorbent systems face many challenges since moisture and heat management are problematic and solid-solid heat exchange is inefficient. Recently, a novel solid sorbent system, the sorbent polymer composite (SPC), has been developed to overcome those challenges in an energy-saving CO 2 capture process using TSA membrane contactors. A SPC material is comprised of a powdered solid sorbent embedded into a hydrophobic and porous polymer matrix. It allows gases to permeate through and achieve full contact with the sorbents while rejecting water moisture in the CO 2 capture process. In this collaborative research, NETL will conduct performance testing of a novel SPC material and EPRI will conduct a cost analysis based on that performance data.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2021

Surfactant-assisted one-pot sample preparation for label-free single-cell proteomics

Large numbers of cells are generally required for quantitative global proteome profiling due to surface adsorption losses associated with sample processing. Such bulk measurement obscures important cell-to-cell variability (cell heterogeneity) and makes proteomic profiling impossible for rare cell populations (e.g., circulating tumor cells (CTCs)). Here we report a surfactant-assisted one-pot sample preparation coupled with mass spectrometry (MS) method termed SOP-MS for label-free global single-cell proteomics. SOP-MS capitalizes on the combination of a MS-compatible nonionic surfactant, n-Dodecyl-β-D-maltoside, and hydrophobic surface-based low-bind tubes or multi-well plates for ‘all-in-one’ one-pot sample preparation. This ‘all-in-one’ method including elimination of all sample transfer steps maximally reduces surface adsorption losses for effective processing of single cells, thus improving detection sensitivity for single-cell proteomics. This method allows convenient label-free quantification of hundreds of proteins from single human cells and ~1200 proteins from small tissue sections (close to ~20 cells). When applied to a patient CTC-derived xenograft (PCDX) model at the single-cell resolution, SOP-MS can reveal distinct protein signatures between primary tumor cells and early metastatic lung cells, which are related to the selection pressure of anti-tumor immunity during breast cancer metastasis. The approach paves the way for routine, precise, quantitative single-cell proteomics.

36 MATERIALS SCIENCE↗

DOE OSTI2023

NMR relaxometry characterization of water adsorption in corn stover anatomical fractions

Nuclear magnetic resonance (NMR) relaxometry is applied to provide direct measurement of water adsorption in anatomical fractions of corn stover. NMR transverse T 2 relaxation time distribution measurements indicate multiple water populations, which vary with anatomical fraction and water adsorption. Measured T 2 data are used to calculate thermodynamic properties of Brunauer-Emmet-Teller adsorption theory using a model to estimate mono and bilayer relaxation. T 2 data are used directly to determine rotational diffusion correlation times indicating adsorption interaction strength. T 1 -T 2 longitudinal-transverse relaxation time correlation measurements quantify differences in the molecular level structural order of the adsorbate surface water as a function of water activity, i.e. relative humidity or water vapor partial pressure. The T 1 /T 2 ratio provides a measure of the surface energy related to the adsorption strength and surface diffusive mobility of the water adsorbate and differentiates the anatomical fractions. Furthermore, the results indicate that direct measurement of NMR relaxation times can be used to characterize corn stover biomass water adsorption, data relevant to processing and handling considerations.

09 BIOMASS FUELS↗

DOE OSTI2021

Nanoscale cooperative adsorption for materials control

Abstract Adsorption plays vital roles in many processes including catalysis, sensing, and nanomaterials design. However, quantifying molecular adsorption, especially at the nanoscale, is challenging, hindering the exploration of its utilization on nanomaterials that possess heterogeneity across different length scales. Here we map the adsorption of nonfluorescent small molecule/ion and polymer ligands on gold nanoparticles of various morphologies in situ under ambient solution conditions, in which these ligands are critical for the particles’ physiochemical properties. We differentiate at nanometer resolution their adsorption affinities among different sites on the same nanoparticle and uncover positive/negative adsorption cooperativity, both essential for understanding adsorbate-surface interactions. Considering the surface density of adsorbed ligands, we further discover crossover behaviors of ligand adsorption between different particle facets, leading to a strategy and its implementation in facet-controlled synthesis of colloidal metal nanoparticles by merely tuning the concentration of a single ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗