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At least 163 records · Page 9

Assessment of Amine-Based CO2BOLs for Direct Air Capture

Direct air capture (DAC) technologies extract CO 2 from the atmosphere for CO 2 storage, or utilization. Capturing CO 2 from the air is the most expensive application of carbon capture because CO 2 in the atmosphere is very dilute. There are limited number of CO 2 capture technologies for DAC application. This project aims at developing an energy efficient technology for DAC, leveraging two PNNL’s chemistries (solid and liquid CO 2 capture). Three CO 2 capture sorbents consisting of amine based CO 2 BOLs immobilized in mesoporous silica were designed, synthesized, and tested. These sorbents had ~ 19-23 wt.% amine loadings which is lower than typical amine-based silica sorbents. The surface area and pore volumes of these solid supported CO 2 BOLs are lower compared to those of the pristine silica support. The CO 2 capture performance of these materials was significantly lower than the typical silica supported amines due to low amine loading and higher molecular weight with low amine density. These results show that immobilize CO 2 BOLs in silica are not viable materials for removing CO 2 from ambient air. This project also designed, synthesized at tested liquid solvents for DAC application. Solvent properties that is vapor pressure, CO 2 uptake capacity, kinetics, and viscosity for three novel solvents were evaluated. The CO 2 uptake capacity for one of the most promising amine-based solvent BEPBEGDA was the highest at 13.2 wt% corresponding to 97 mol%. The vapor pressure of the BEPBEGDA solvents were very low at 80 °C compared to other solvents making them suitable for DAC application. The effect of humidity on the CO 2 capture performance of these solvents was evaluated which shows that presence of moisture doesn’t have a negative effect on the CO 2 uptake performance but makes it slightly better. The performances of these solvents were slightly below that of the 0.1M NaOH solution tested under similar conditions. Despite of the slightly lower CO 2 uptake, it is expected that these liquid solvents will have lower regeneration temperature and minimum evaporative losses due their low vapor pressure. Future work will focus on optimization of the liquid solvents for DAC application to improve both CO 2 capture efficiency and capacity without viscosity and vapor pressure increase. Testing of these solvents under DAC conditions using a gas liquid contactor that mimic industrial applications is needed. Solvent cost projection, techno-economic analysis and life cycle analysis are required to evaluate economic viability of this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Air Capture Using Trapped Small Amines in Hierarchical Nanoporous Capsules on Porous Electrospun Fibers (Final Technical Report)

This report summarizes the carbon capture research and development conducted by The State University of New York at Buffalo (UB) and GTI Energy (GTI) for award “DE-FE0031969: Direct Air Capture Using Trapped Small Amines in Hierarchical Nanoporous Capsules on Porous Electrospun Fibers” sponsored by the U.S. Department of Energy (DOE). The objective of this project is to develop an innovative sorbent structure of trapped small amines in HNC embedded in PEF for DAC. This involves tailoring both sorbent and PEF materials to achieve a compact system for DAC with high capacity for CO 2 at concentrations typically available in air and at near ambient conditions. An innovative sorbent structure of trapped small amines in hierarchical nanoporous capsules (HNC) embedded in porous electrospun fibers (PEF) was developed for direct air capture (DAC). This involves tailoring both sorbent and PEF materials to achieve a compact system for DAC with high capacity for CO 2 at concentrations typically available in air and at near ambient conditions. An interfacial polymerization process was developed, which utilized loaded amines inside mesoporous silica and trimesoyl chloride (TMC) dissolved in organic solvents as the precursors, to generate a polyamide (PA) coating layer on mesoporous silica and thus trap amines. Reaction conditions, including TMC concentration, organic solvents, reaction time, etc., for interfacial polymerization were optimized to effectively trap loaded amines, and cyclic heating-cooling operation was conducted to evaluate the coating quality. Larger pore volume mesoporous silica was also synthesized to increase amine loading and thus increase CO 2 capacity. The optimized sorbent material exhibited CO 2 capacity as high as 4.88 mmol/g under humid DAC conditions and negligible loss (<1%) during 10 cyclic heating-cooling operations. The optimized PA-coated sorbent also showed fast adsorption and desorption kinetics, with <20% t1/2 increase compared to uncoated sorbent. PEF fabrication conditions, including organic solvents for dissolving core and shell polymers, voltage, distance from the nozzle to the collection panel, etc. were adjusted to better incorporate HNC. After incorporating the optimized sorbent material into PEF, the structured sorbent had a CO 2 capacity of approximately 4.0 mmol/g under humid DAC conditions, with capacity loss of 0.17% per cycle and t1/2 increase less than 10%. A techno-economic analysis (TEA) for the process design for a DAC system based on our developed sorbent structure of trapped small amines in HNC embedded in PEF was conducted. The process design included process description and major equipment sizing and energy and mass balances in addition to scale-up research results and estimated capture cost. Aspen Adsorption Simulator was used to fit the experimentally measured breakthrough curves and extract equilibrium and kinetic data of the optimized sorbent. Our results indicated that for a DAC plant with CO 2 productivity of 3,000 tonne/year, the levelized cost of CO 2 capture was $\$$612/tonne, with the largest contribution of 44.33% from the fixed operation cost. Increasing CO 2 productivity, while maintaining similar fixed operation cost, is expected to significantly reduce the CO 2 capture cost. A sensitivity study was also conducted to understand the influence of total plant cost, sorbent cost, CO 2 concentration in the feed, sorbent mat lifetime, sorbent regeneration electricity, and adsorption blower pressure drop on the levelized cost of CO 2 capture, revealing a capture cost range of $\$$520-870/tonne.

36 MATERIALS SCIENCE↗

Impact of Oxygen Storage Components in Prototype Pd-Based Three-Way Catalysts under Exhaust Conditions Relevant to Propane Engines

With increasing concerns about global warming, the push for sustainable and eco-friendly fuels is accelerating. Propane, recognized as liquefied petroleum gas or LPG, has garnered research interest as an alternative fuel due to its notable advantages, including a high-octane rating, reduced greenhouse gas emissions, and potential cost-effectiveness. However, to realize its full potential as an alternative fuel it is essential to develop catalysts that efficiently handle emissions at low temperatures. In our research, we investigated three distinct palladium (Pd)-based three-way catalyst (TWC) formulations (PdRh, Pd-only, and Pd-OSC) to investigate the influence of typical TWC components rhodium (Rh) and oxygen storage components (OSC) in exhaust scenarios relevant to propane-fueled engines. Among these, the formulation containing oxygen storage components (Pd-OSC) showed the highest reactivity for both NO and C 3 H 8 while minimizing performance degradation from hydrothermal aging (HTA). Notably, the temperature of 50% conversion (T50) for propane in the Pd-OSC fresh and HTA sample was lower by 30 °C and 13 °C, respectively, compared to the Pd-only sample, highlighting the role of oxygen storage materials in enhancing catalyst performance, even without dithering. Additionally, N 2 physisorption showed that the PdOSC sample has a higher surface area and increased pore volume. This underscores the idea that OSC materials not only augment the catalyst’s porosity but also optimize reactant accessibility to active sites, thus elevating catalytic efficiency. In addition to evaluating performance, we further explored the performance and characteristics of the catalysts using catalytic probe reactions, such as water–gas shift and steam reforming reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen, Methane, Brine Flow Behavior, and Saturation in Sandstone Cores During H 2 and CH 4 Injection and Displacement

Large-scale underground hydrogen storage (UHS) is a critical component in the emerging hydrogen economy. Knowledge of multiphase flow behavior involving hydrogen in storage reservoir formations is crucial to characterizing hydrogen transport properties and essential for the deliverability and storage operations of UHS. There are still many gaps in fully understanding hydrogen–methane–brine multiphase phase flow that require further investigation. In this work, H 2 and CH 4 were injected through brine-saturated sandstone cores using a tri-axial core holder system fitted with flow rate meters and pressure transducers, while the effluent gas concentrations were analyzed using an online micro gas chromatograph. Brine displacement, permeability, and gas breakthrough curves were measured. We studied the flow behavior of hydrogen and methane in sandstone cores through testing brine displacement by gas injection and comparing the hydrogen displacement of methane with the methane displacement of hydrogen. We also tested the differences between horizontal and vertical flow in brine displacement. The results showed that brine displacement was more efficient in a core with higher permeability and porosity, resulting in a higher initial gas saturation. A higher gas injection rate brought about faster gas breakthrough measured by pore volume and sharper concentration curves. Hydrogen did not exhibit abnormal flow in the sandstone when the flow was horizontal and downward vertical. Gas overriding was observed in brine displacements when the flow was horizontal, with hydrogen showing this behavior more profoundly compared to methane. Downward vertical gas injection induced higher efficiency brine displacement compared to horizontal displacement and resulted in a higher initial gas saturation in the sandstone cores. These findings address critical knowledge gaps regarding gas flow patterns and displacement behaviors during hydrogen injection and recovery phases in UHS facilities using methane as the cushion gas. The insights from this research offer valuable guidance for optimizing UHS systems, ensuring operational efficiency, and advancing sustainable energy solutions in alignment with decarbonization goals.

08 HYDROGEN↗

Hybrid Mesoporous Carbon/Copper Ferrite Electrode for Asymmetric Supercapacitors

Asymmetric supercapacitors (ASCs) with two dissimilar electrodes are known to exhibit relatively moderate energy and power densities. If electrodes derived from earth-abundant materials or renewable resources such as lignocellulosic biomass (LCB) are used for fabrication, energy storage systems are expected to become less expensive and more sustainable. Hybrid electrode materials have advantages such as higher surface area, better chemical stability, and superior energy density. This study reports on the synthesis of a novel hybrid electrode material containing porous carbon (POC) and copper ferrite, which is designated as POC@Cu-ferrite, and its electrochemical performance in ASC configuration. Corn stover derived hydrochar is utilized for the sol–gel synthesis of POC@Cu-ferrite hybrid material using earth-abundant Cu and Fe-based precursors. This material is characterized using X-ray diffraction (XRD), Raman spectroscopy, Brunauer–Emmett–Teller (BET) surface area analyzer, and scanning and transmission electron microscopy (SEM/TEM). As-synthesized Cu-ferrite is found to contain 89.2% CuFe 2 O 4 and 10.8% Fe 2 O 3 , whereas other phases such as Fe 3 O 4 , CuFeO 2 , and CuO are observed for the POC@Cu-ferrite. BET-specific surface area (SSA) and pore volume of POC@Cu-ferrite are observed as 1068 m 2 /g and 0.72 cm 3 /g, respectively. POC@Cu-ferrite hybrid electrode is used with POC opposite electrode to fabricate ASC, which is tested using Gamry G-300 potentiostat/galvanostat/ZRA to obtain cyclic voltammetry (CV) profiles and galvanostatic charge–discharge (GCD) plots. ASC is also prepared using Cu-ferrite and POC materials and its specific capacitance and stability are compared with ASCs prepared with POC@Cu-ferrite and POC or graphene nanoplatelets (GNPs) electrodes. POC@Cu-ferrite hybrid electrode is found to be superior with a 2-fold higher capacitance and significant electrochemical stability over 100 GCD cycles as compared to the Cu-ferrite electrode.

36 MATERIALS SCIENCE↗

ARM Data for Examining the Ice-Nucleating Particles from SGP Part II (ExINP-SGP II) X-Ray Diffraction

Knowledge of airborne particulate matter (PM), especially the particles that have supermicron diameters, is key for understanding ice-nucleating particles (INPs). Supported by the Atmospheric Radiation Measurement (ARM) user facility, we sampled PM and surface soil materials at the Southern Great Plains observatory (SGP; 36&deg; 36&prime; 18&Prime; N, 97&deg; 29&prime; 6&Prime; W) to systematically compare the INP abundance and ice nucleation efficiency of different SGP samples (i.e., airborne versus surface materials). The field campaign, named Examing INP from SGP II (ExINP-SGP II), was conducted from 20 January to 20 April, 2021. Our data analysis products include (1) physical surface sorption characterization data (i.e., BET, pore volume) of two sets of samples -- SGP Soil and USDA, (2) X-ray diffraction spectra for the same two samples, (3) immersion freezing assay-based ice nucleation active mass density data as a function of freezing temperature for both ambient and surface samples, and (4) time-series data of ambient meteorological conditions, concentration particle counter-derived aerosol particle concentration, and aerosol particle sizer measurement during ExINP-SGP II.

54 ENVIRONMENTAL SCIENCES↗

ARM Data for Examining the Ice-Nucleating Particles from SGP Part II (ExINP-SGP II) Cryogenic Refrigerator Applied to Freezing Test

Knowledge of airborne particulate matter (PM), especially the particles that have supermicron diameters, is key for understanding ice-nucleating particles (INPs). Supported by the Atmospheric Radiation Measurement (ARM) user facility, we sampled PM and surface soil materials at the Southern Great Plains observatory (SGP; 36&deg; 36&prime; 18&Prime; N, 97&deg; 29&prime; 6&Prime; W) to systematically compare the INP abundance and ice nucleation efficiency of different SGP samples (i.e., airborne versus surface materials). The field campaign, named Examing INP from SGP II (ExINP-SGP II), was conducted from 20 January to 20 April, 2021. Our data analysis products include (1) physical surface sorption characterization data (i.e., BET, pore volume) of two sets of samples -- SGP Soil and USDA, (2) X-ray diffraction spectra for the same two samples, (3) immersion freezing assay-based ice nucleation active mass density data as a function of freezing temperature for both ambient and surface samples, and (4) time-series data of ambient meteorological conditions, concentration particle counter-derived aerosol particle concentration, and aerosol particle sizer measurement during ExINP-SGP II.

54 ENVIRONMENTAL SCIENCES↗

ARM Data for Examining the Ice-Nucleating Particles from SGP Part II (ExINP-SGP II) Aerodynamic Particle Sizer, Condensation Particle Counter, and Meteorological Instrument Data Analysis

Knowledge of airborne particulate matter (PM), especially the particles that have supermicron diameters, is key for understanding ice-nucleating particles (INPs). Supported by the Atmospheric Radiation Measurement (ARM) user facility, we sampled PM and surface soil materials at the Southern Great Plains observatory (SGP; 36&deg; 36&prime; 18&Prime; N, 97&deg; 29&prime; 6&Prime; W) to systematically compare the INP abundance and ice nucleation efficiency of different SGP samples (i.e., airborne versus surface materials). The field campaign, named Examing INP from SGP II (ExINP-SGP II), was conducted from 20 January to 20 April, 2021. Our data analysis products include (1) physical surface sorption characterization data (i.e., BET, pore volume) of two sets of samples -- SGP Soil and USDA, (2) X-ray diffraction spectra for the same two samples, (3) immersion freezing assay-based ice nucleation active mass density data as a function of freezing temperature for both ambient and surface samples, and (4) time-series data of ambient meteorological conditions, concentration particle counter-derived aerosol particle concentration, and aerosol particle sizer measurement during ExINP-SGP II.

54 ENVIRONMENTAL SCIENCES↗

Single-cell protein from waste cellulose

The recycle, reuse, or reclamation of single cell protein from liquid and solid agricultural waste fibers by a fermentation process is reported. It is shown that cellulose comprises the bulk of the fibers at 50% to 55% of the dry weight of the refuse and that its biodegradability is of prime importance in the choice of a substrate. The application of sodium hydroxide followed by heat and pressure serves to de-polymerize and disrupt lignin structure while swelling the cellulose to increase water uptake and pore volume. Some of the lignin, hemi-celluloses, ash, and cellulose of the material is hydrolized and solubilized. Introduction of microorganisms to the substrate fibers mixed with nutrients produces continuous fermentation of cellulose for further protein extraction and purification.

Dunlap, C. E.↗

Pore Structure Analysis of RSI Tile

Mercury porosimetry gives a means of characterizing RSI tile pore structure in terms of porosity, pore size distribution, bulk density, specific surface area, mean pore diameter, and mean fiber diameter. It also allows the determination of the effects of heat treatment on these parameters. It is limited in application to open-pored structures, however, since any closed pore volume is ignored.

Whittemore, O. J., Jr.↗

Water vapor weathering of Taurus-Littrow orange soil - A pore-structure analysis

A pore-volume analysis was performed on water vapor adsorption data previously obtained on a fresh sample of Taurus-Littrow orange soil, and the analysis was repeated on the same sample after its exposure to moist air for a period of approximately six months. The results indicate that exposure of an outgassed sample to high relative pressures of water vapor can result in the formation of substantial micropore structure, the precise amount being dependent on the sample pretreatment, particularly the outgassing temperature. Micropore formation is explained in terms of water penetration into surface defects. In contrast, long-term exposure to moist air at low relative pressures appears to reverse the process with the elimination of micropores and enlargement of mesopores possibly through surface diffusion of metastable adsorbent material. The results are considered with reference to the storage of lunar samples.

Cadenhead, D. A.↗

Coal desulfurization by chlorinolysis production and combustion test evaluation of product coals

Laboratory-scale screening tests were carried out on coal from Harrison County, Ohio to establish chlorination and hydrodesulfurization conditions for the batch reactor production of chlorinolysis and chlorinolysis-hydrodesulfurized coals. In addition, three bituminous coals, were treated on the lab scale by the chlorinolysis process to provide 39 to 62% desulfurization. Two bituminous coals and one subbituminous coal were then produced in 11 to 15 pound lots as chlorinolysis and hydrodesulfurized coals. The chlorinolysis coals had a desulfurization of 29-69%, reductions in voltatiles and hydrogen. Hydrodesulfurization provided a much greater desulfurization (56-86%), reductions in volatiles and hydrogen. The three coals were combustion tested in the Penn State ""plane flame furnace'' to determine ignition and burning characteristics. All three coals burned well to completion as: raw coals, chlorinolysis processed coals, and hydrodesulfurized coals. The hydrodesulfurized coals experienced greater ignition delays and reduced burning rates than the other coals because of the reduced volatile content. It is thought that the increased open pore volume in the desulfurized-devolatilized coals compensates in part for the decreased volatiles effect on ignition and burning.

Kalvinskas, J. J.↗

Heats of immersion of titania powders in primer solutions

The oxide layer present on titanium alloys can play an important role in determining the strength and durability of adhesive bonds. Here, three titania powders in different crystalline phases, rutile-R1, anatase-A1, and anatase-A2, are characterized by several techniques. These include microelectrophoresis, X-ray diffractometry, surface area pore volume analysis, X-ray photoelectron spectroscopy, and measurements of the heats of immersion. Of the three powders, R1 has the highest heat of immersion in water, while the interaction between water and A1 powder is low. Experimental data also suggest a specific preferential interaction of polyphenylquinoxaline with anatase.

Siriwardane, R.↗

KOH concentration effect on the cycle life of nickel-hydrogen cells. 4: Results of failure analyse

Effects of KOH concentrations on failure modes and mechanisms of nickel-hydrogen cells were studied using long cycled boiler plate cells containing electrolytes of various KOH concentrations ranging 21 to 36 percent. Life of these cells were up to 40,000 cycles in an accelerated low earth orbit (LEO) cycle regime at 80 percent depth of discharge. An interim life test results were reported earlier in J. Power Sources, 22, 213-220, 1988. The results of final life test, end-of-life cell performance, and teardown analyses are discussed. These teardown analyses included visual observations, measurements of nickel electrode capacity in an electrolyte-flooded cell, dimensional changes of cell components, SEM studies on cell cross section, BET surface area and pore volume distribution in cycled nickel electrodes, and chemical analyses. Cycle life of a nickel-hydrogen cell was improved tremendously as KOH concentration was decreased from 36 to 31 percent and from 31 to 26 percent while effect of further concentration decrease was complicated as described in our earlier report. Failure mode of high concentration (31 to 36 percent) cells was gradual capacity decrease, while that of low concentration (21 to 26 percent) cells was mainly formation of a soft short. Long cycled (25,000 to 40,000 cycles) nickel electrodes were expanded more than 50 percent of the initial value, but no correlation was found between this expansion and measured capacity. All electrodes cycled in low concentration (21 to 26 percent) cells had higher capacity than those cycled in high concentration (31 to 36 percent) cells.

Lim, H. S.↗

Evidence for the abundance of water on Mars now and in the past

This paper discusses evidence for the abundance of water on Mars early in its history, based on the analysis of the Viking 1 and 2 images and the Martian-atmosphere water measurements. It is argued that integrated networks of small valleys in the ancient cratered terrain of Mars may indicate that the planet once possessed a warmer climate. It is pointed out that most Martian outflow channels originate from the regions of collapsed and disrupted terrain, suggesting that they were formed by a catastrophic release of groundwater. The question of the fate of Martian water is discussed, and arguments are presented suggesting that the Martian crust may retain significant porosity to a depth of 10 km and may possess a total pore volume sufficient to store a global layer of water 0.5-1.5 km deep.

Clifford, Stephen M.↗

Mechanical strength and thermophysical properties of PM212: A high temperature self-lubricating powder metallurgy composite

A powder metallurgy composite, PM212, composed of metal bonded chromium carbide and solid lubricants is shown to be self-lubricating to a maximum application temperature of 900 C. The high temperature compressive strength, tensile strength, thermal expansion and thermal conductivity data needed to design PM212 sliding contact bearings and seals are reported for sintered and isostatically pressed (HIPed) versions of PM212. Other properties presented are room temperature density, hardness, and elastic modulus. In general, both versions appear to have adequate strength to be considered as sliding contact bearing materials, but the HIPed version, which is fully dense, is much stronger than the sintered version which contains about 20 percent pore volume. The sintered material is less costly to make, but the HIPed version is better where high compressive strength is important.

Edwards, Phillip M.↗

High surface area, low weight composite nickel fiber electrodes

The energy density and power density of light weight aerospace batteries utilizing the nickel oxide electrode are often limited by the microstructures of both the collector and the resulting active deposit in/on the collector. Heretofore, these two microstructures were intimately linked to one another by the materials used to prepare the collector grid as well as the methods and conditions used to deposit the active material. Significant weight and performance advantages were demonstrated by Britton and Reid at NASA-LeRC using FIBREX nickel mats of ca. 28-32 microns diameter. Work in our laboratory investigated the potential performance advantages offered by nickel fiber composite electrodes containing a mixture of fibers as small as 2 microns diameter (Available from Memtec America Corporation). These electrode collectors possess in excess of an order of magnitude more surface area per gram of collector than FIBREX nickel. The increase in surface area of the collector roughly translates into an order of magnitude thinner layer of active material. Performance data and advantages of these thin layer structures are presented. Attributes and limitations of their electrode microstructure to independently control void volume, pore structure of the Ni(OH)2 deposition, and resulting electrical properties are discussed.

Johnson, Bradley A.↗

Temporal changes in the geographic distribution, elevation, and potential origin of the Martian outflow channels

Observational evidence of outflow channel activity on Mars suggests that water was abundant in the planet's early crust. However, with the decline in the planet's internal heat flow, a freezing front developed within the regolith that propagated downward with time and acted as a thermodynamic sink for crustal H2O. One result of this thermal evolution is that, if the initial inventory of water on Mars was small, the cryosphere may have grown to the point where all the available water was taken up as ground ice. Alternatively, if the inventory of H2O exceeds the current pore volume of the cryosphere, then Mars has always possessed extensive bodies of subpermafrost groundwater. We have investigated the relative age, geographic distribution, elevation, and geologic setting of the outflow channels in an effort to accomplish the following: (1) identify possible modes of origin and evolutionary trends in their formation; (2) gain evidence regarding the duration and spatial distribution of groundwater in the crust; and (3) better constraint estimates of the planetary inventory of H2O.

Tribe, S.↗