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At least 91 records · Page 5

Hydroxyl radical yields in the heavy ion radiolysis of water

Scavenging experiments coupled with Monte Carlo track structure and kinetics simulations have been used to determining and understand the yields of hydroxyl radicals in the radiolysis of water with protons and carbon ions. Carbon dioxide production from aerated formic acid solutions with concentrations ranging from 10-3 to 1 mol./dm3 was used as a probe of the time dependence of the hydroxyl radical yield from about 5 ns to 1 ?s. Numerical extrapolation of the results at slightly different ion energies in combination with data from gamma radiolysis experiments allows a systematic analysis of both track average and track segment yields, with considerable track chemistry found to occur on the nanosecond to microsecond time scale. Track chemistry calculations utilizing Monte Carlo track structure simulations and nonhomogeneous independent reaction times diffusion-reaction modeling of product yields reproduce experimental observations. Subsequently, the track simulation methods were used to predict hydroxyl radical kinetics in deaerated and aerated water at neutral pH. Taken with literature data for helium ion beam studies, the results offer insight into the potential for indirect radiation induced damage to biological systems for light ions with very different track structures.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Semi‐Continuous Ex Situ Carbon Dioxide Mineralization in Produced Water for Calcite Production

ABSTRACT The mineralization of carbon dioxide (CO 2 ) to stable carbonate products is a desirable process for carbon capture utilization and storage (CCUS). However, improving the process economics through creative use of available reactants is necessary to develop a scalable mineralization process. This study details the development of a semi‐continuous CO 2 mineralization process that uses flue gas as a point CO 2 source, produced water (PW) as an alkaline source of Ca 2+ , and NaOH effluent (potentially sourced from integration with the chlor‐alkali process. Operating at a controlled pH allowed for both complete reaction of available Ca 2+ (100% carbonation potential or 9.9 g CO 2 .L –1 PW brine) and for reproducible control of the produced calcium carbonate (CaCO 3 ) product. A full factorial design of experiments was implemented to study the effects of reaction temperature, pH, and gaseous CO 2 concentration on the mineralization and CO 2 capture rates as well as product crystalline structure and morphology. A maximum CO 2 capture rate of 0.315 ± 0.007 kg.L –1 .d –1 was achieved at 25°C and 25% CO 2 . CO 2 gas to liquid phase mass transport is believed to be the rate limiting step. With improved reactor design and optimization, the proposed semi‐continuous mineralization process shows promise for scaling to a pilot scale CO 2 capture technology.

Bennett, Quinn [Institute for Sustainable Energy &↗

Extracellular electron transfer across bio-nano interfaces for CO 2 electroreduction

Acetogenic bacteria represent a class of organisms capable of converting reducing equivalents and carbon dioxide into products with carbon–carbon bonds. Materials-based bio-electrochemical approaches are attractive for supplying biological organisms directly with grid-supplied electrons to convert carbon dioxide to value-added chemicals. Carbon nanotube-modified biocathodes have emerged as promising candidates for microbial electrosynthesis with high yields of carbon product formation, but a fundamental understanding of extracellular charge transfer at this electrode-biofilm interface is still lacking. Here, we utilize solid-state interfaces between semiconducting single-walled carbon nanotubes (s-SWCNT) and a model acetogenic bacterium for mechanistic studies of electro-catalytic CO 2 conversion to acetate. Studies of bacteria/s-SWCNT interactions in a transistor-based device suggest direct extracellular electron transfer (EET) at the bio-nano interface. Deuterium isotope labeling experiments confirmed that the availability of electrochemically produced H 2 as a redox mediator does not limit the efficiency of EET and CO 2 electro-reduction for C. ljungdahlii biofilms, suggesting the primary reducing equivalents are the electrons delivered across the electrode/bacterium interface or involvement of biological redox mediators. Additional isotope labeling studies demonstrate high Faradaic efficiency for CO 2 electro-reduction at the SWCNT/bacterium interface. These results provide important information about EET across the bacterium/material interface in a model biocathode.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Systems and methods for biological conversion of carbon dioxide pollutants into useful products

Methods and systems to achieve clean fuel processing systems in which carbon dioxide emissions (1) from sources (2) may be processed in at least one processing reactor (4) containing a plurality of chemoautotrophic bacteria (5) which can convert the carbon dioxide emissions into biomass (6) which may then be used for various products (21) such as biofuels, fertilizer, feedstock, or the like. Sulfate reducing bacteria (13) may be used to supply sulfur containing compounds to the chemoautotrophic bacteria (5).

09 BIOMASS FUELS↗

A Scalable Process for Upcycling Carbon Dioxide (CO 2 ) and Coal Combustion Residues into Construction Products

Anthropogenic sources of carbon dioxide are generated from a number of sources, but the key among these are ordinary Portland cement (OPC) production and combustion of fossil fuels. Cement production is the largest global CO 2 source from the mineral decomposition of carbonates. Combination of the limestone decomposition and thermal requirements of the clinkering process causes cement production to contribute 8-9% of annual global CO 2 emissions. Combustion of fossil fuels (coal, oil and gas) was shown to contribute a much larger portion of global CO 2 emissions. As of 2018, combustion of fossil fuels accounted for 65% of global CO 2 , where 41% was derived from stationary sources for electricity and heat generation and the other 24% was related to transport. To reduce these contributions, key steps forward in CO 2 utilization technologies are required. The purpose of this project is to demonstrate the feasibility of the Reversa process evolving from a TRL-3 technology at the bench-scale up to TRL-6 technology at the pilot-scale. The reliability of the Reversa technology was tested to prove the effective production of concrete masonry units (CMUs) at bench scale, where the units exceeded the required 13.8 MPa compressive strength requirements. The overall goal of this project was to accelerate the development of a CO 2 mineralization process that synergistically utilizes CO 2 in flue gas and coal combustion residues (CCRs) to synthesize carbonated concrete, a functional replacement for traditional concrete. The culmination of this work resulted in 12 successful production runs at the Integrated Test Center (ITC), Gillette, WY using coal flue gas as a CO 2 source. This was followed by 6 production runs which were completed at the National Carbon Capture Center (NCCC), Wilsonville, AL, using coal-fired and natural gas (NG) flue gas as the CO 2 source. Over the course of the production runs at NCCC and ITC, the CO 2 utilization as a function of time, 24-h CO 2 uptake, electricity usage, and 28-d net area compressive strength recorded for each run. The ITC and NCCC demonstrations achieved an average of 0.19 and 0.1 g CO 2 /g reactant, respectively. Both demonstrations exceeded the project’s target goals of uptake > 0.05 g CO 2 /g reactant. Average compressive strength of the ITC blocks was 18.24 MPa at 28-days. This exceeded the target strength of 13.8 MPa specified by ASTM C90. ITC and NCCC produced an average CO 2 utilization efficiency of 74.9 and 57.9%, respectively. Both demonstration averages were within the target range of 50 to 90% utilization efficiency. For some production runs the NCCC demo did exceeded the a CO 2 utilization efficiency of 75%. An LCA of the Reversa process compared to an industry standard product revealed a net CO 2 reduction of 39% to 42%. This exceeded the target requirement of >25% net CO 2 reduction. Collection of this data was used to determine that the project was successful as the demonstration goals were achieved: (1) achieving in excess of 75% CO 2 utilization efficiency, (2) utilizing greater than 250 kg of CO 2 per production batch/run, and (3) ensuring compliance of carbonated blocks with industry standard specifications (ASTM C90).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carbon dioxide and water vapor production at rest and during exercise. A report on data collection for the Crew and Thermal Systems Division

The current environmental control device in the shuttle uses lithium hydroxide (LiOH) filter canisters to remove carbon dioxide (CO2) from the cabin air, requiring several bulky filter canisters that can only be used once and must be changed frequently. To alleviate a stowage problem and decrease launch weight, the Crew and Thermal Systems Division (CTSD) at the NASA Johnson Space Center has been researching a system to be used on future shuttle missions. This system uses two beds of solid amine material to absorb CO2 and water, later desorbing them to space vacuum. In this way the air scrubbing medium is regenerable and reusable. To identify the efficacy of this regenerable CO2 removal system (RCRS), CTSD began investigations in the shuttle mockup. The purpose of this investigation was to support the CTSD program by determining mean levels of carbon dioxide and water vapor production in normal, healthy males and females age-matched with the astronaut corps. Subjects' responses were measured at rest and during exercise at intensity levels equivalent to normal shuttle operation activities. The results were used to assess the adjustments made to RCRS and are reported as a reference for future investigations in shuttle environmental control.

Lee, Stuart M. C.↗

Prospects of hydrogen cogeneration and carbon dioxide utilization in electrochemical refineries for ethylene production via oxidative coupling of methane: A techno-economic assessment

Ethylene is recognized as one of the most significant chemicals globally. The projected ethylene production for 2023 stands at 227.6 million tonnes, with expectations of continued demand growth. The primary use of ethylene, accounting for over 76%, lies in the production of plastics such as polyethylene, polyvinyl chloride, and polystyrene. Despite the enduring carbon retention potential of plastics themselves, traditional ethylene feedstock production from fossil resources contributes substantially to greenhouse gas emissions, ranging from 0.29 to 2.29 kg CO2 /kg Ethylene depending on various factors like feedstock and process design. Various decarbonization strategies, including the utilization of hydrogen as a primary heat source, have been proposed to reduce the carbon footprint of ethylene production, but their efficacy remains limited, offering at best a 0–30% reduction in on-site CO 2 emissions.

09 BIOMASS FUELS↗

Mangrove peat and algae leachates elicit rapid and contrasting molecular and microbial responses in coastal waters

Abstract As sea level rises, previously sequestered blue carbon can be exported offshore as particulate or dissolved organic matter where it may be re-mineralized or sequestered. The priming effect, or interactive effects of organic matter turnover with a mixed substrate, is well described in soils, but still debated in aquatic systems. Priming may contribute to enhanced blue carbon re-mineralization in coastal environments. Here we examined mangrove-derived dissolved organic matter turnover in a lab incubation, with leachates from mangrove peat, 13 C-labeled algae, and peat+algae (primed). Particulate and dissolved organic matter were assessed; microbial metatranscriptomes were evaluated; and dissolved organic matter was characterized with high resolution mass spectrometry. Stable isotopes indicated rapid allocation of algal-derived dissolved organic matter into particulate organic matter. The algal treatment had the greatest increase in carbon dioxide, but primed and peat treatments had the greatest loss of dissolved organic carbon, greater RNA concentrations, and similar changes in total carbon dioxide. This suggests that, while total carbon dioxide did not increase under priming conditions, the addition of a peat substrate may promote microbial biomass production relative to carbon dioxide production. This work highlights that more targeted studies investigating the specific mechanisms of priming are necessary to address the molecular and microbial transformations associated with priming in aquatic systems.

54 ENVIRONMENTAL SCIENCES↗

A recirculation system for concentrating CO 2 electrolyzer products

Electrochemical carbon dioxide reduction represents a promising path to utilize CO 2 as a feedstock for generating valuable products such as fuels and chemicals. Faradaic efficiencies near 100% have been achieved for certain CO 2 reduction products such as CO, but the electrolyzer outlet streams usually contain large fractions of unreacted CO 2 , dropping the product concentrations below 1% in many cases. The system disclosed here recycles the unreacted CO 2 together with the products and flows them back into the CO 2 reduction reactor, enabling much higher CO 2 conversion rates without dropping the gas flow rate. However, simple recirculation is shown to accumulate significant amounts of hydrogen, impeding effective CO 2 reduction. In this looped system, an electrochemical H 2 pump is placed in series with the CO 2 reactor, which effectively removes all the H 2 from the recycled gas stream, increasing the concentrations of carbon-containing products. Here, the system was initially tested with a CO-generating catalyst and CO concentrations above 70% were achieved in the recycled gas stream, compared to a maximum CO concentration of 8% in single-pass configuration. Results with a CO 2 reactor targeting ethylene as the main product show that ethylene concentrations of at least 10% can be achieved, which is roughly 20 times higher compared to a single-pass system.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Comparative Life Cycle Analysis of Carbon Dioxide Utilization in Concrete Products

In this study, a comparative LCA of CO2U concrete processes is conducted, revealing promise in several research areas. The environmental impacts of replacing conventional binder and aggregates with carbonated steel slag and direct carbonation of concrete are investigated in ten different product systems, which include both ready-mix and pre-cast concretes. The results indicate that cement substitution, CO2 uptake, electricity consumption, and the electricity grid mix constitute critical levers for deep decarbonization of concrete building materials. This presentation applies LCA to inform the use of CO2U concrete technology pathways in the design of sustainable concrete while promoting transparency and rational assumptions in the presence of uncertainty. Broader themes in the work include LCA of emerging technologies and the sensitivity of LCA results to co-product management methods.

Clarke, James↗

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Oxygen recovery↗

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50% because half of the hydrogen used in the Sabatier reactor is lost as methane which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon, is capable of recovering all the oxygen from carbon dioxide, and it is a promising alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon, and the resulting carbon buildup eventually fouls the catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

ECLSS↗

Self-Cleaning Boudouard Reactor for Full Oxygen Recovery from Carbon Dioxide

Oxygen recovery from respiratory carbon dioxide is an important aspect of human spaceflight. Methods exist to sequester the carbon dioxide, but production of oxygen needs further development. The current International Space Station Carbon Dioxide Reduction System (CRS) uses the Sabatier reaction to produce water (and ultimately breathing air). Oxygen recovery is limited to 50 because half of the hydrogen used in the Sabatier reactor is lost as methane, which is vented overboard. The Bosch reaction, which converts carbon dioxide to oxygen and solid carbon is capable of recovering all the oxygen from carbon dioxide, and is the only real alternative to the Sabatier reaction. However, the last reaction in the cycle, the Boudouard reaction, produces solid carbon and the resulting carbon buildup will eventually foul the nickel or iron catalyst, reducing reactor life and increasing consumables. To minimize this fouling and increase efficiency, a number of self-cleaning catalyst designs have been created. This paper will describe recent results evaluating one of the designs.

Oxygen Recovery↗

Noble-Metal-Free, Nickel-Based Dual Functional Materials for Improved Methane Production from In Situ Carbon Dioxide Capture and Conversion

Promoters for dual functional materials have not been well explored, but promoters could improve the efficiency of the process by improving the selectivity of the CO 2 methanation process. Utilizing integrated capture and conversion, where CO 2 is captured and converted to useful products, would allow for a useful avenue to control CO 2 emissions. One such way to accomplish this would be to utilize materials that can both capture and convert CO 2 to useful products. However, these materials are often based on costly noble metals, like ruthenium and platinum, decreasing their viability on an industrial scale. Less expensive metals, for example, nickel, would allow for dual functional materials to be more readily utilized in industrial settings. Nickel-based dual functional materials often do not react with the captured CO 2 and merely desorb the CO 2 rather than form a useful product. However, promoters have not been well explored for these types of materials to improve the catalytic properties, which would be beneficial to improve nickel-based materials. Herein, we report the addition of ytterbium on a nickel-based dual functional material and the improvements to the production of methane from captured CO 2 with the incorporated ytterbium promoter. The ytterbium promoter improves the selectivity of the catalysts for the hydrogenation of captured CO 2 to methane and increases the ability for the material to capture CO 2 due to additional basic sites being formed on the surface of alumina. As a result, the 12%Ni/4%Yb/6%Na 2 O/Al 2 O 3 catalyst was utilized to capture carbon dioxide and then convert the captured CO 2 to methane over five cycles, where both the amount captured and the amount converted remained stable, indicating the stability of the material over long-term use.

Catalysts↗

CELSS research and development program

Research in Controlled Ecological Life Support Systems (CELSS) conducted by NASA indicate that plant based systems are feasible candidates for human support in space. Ames has responsibility for research and development, systems integration and control, and space flight experiment portions of the CELSS program. Important areas for development of new methods and technologies are biomass production, waste processing, water purification, air revitalization, and food processing. For the plant system, the approach was to identify the flexibility and response time for the food, water, and oxygen production, and carbon dioxide consumption processes. Tremendous increases in productivity, compared with terrestrial agriculture, were realized. Waste processing research emphasizes recycle (transformation) of human wastes, trash, and inedible biomass to forms usable as inputs to the plant production system. Efforts to improve efficiency of the plant system, select new CELSS crops for a balanced diet, and initiate closed system research with the Crop Growth Research Chambers continue. The System Control and Integration program goal is to insure orchestrated system operation of the biological, physical, and chemical operation of the biological, physical, and chemical component processors of the CELSS. Space flight studies are planned to verify adequate operation of the system in reduced gravity or microgravity environments.

Bubenheim, David↗

A Phenazine‐Based Two‐Dimensional Covalent Organic Framework for Photochemical CO 2 Reduction with Increased Selectivity for Two‐Carbon Products

Abstract The reduction of carbon dioxide (CO₂) into valuable products will contribute to sustainable carbon use. Here we report the photocatalytic reduction of CO₂ to carbon monoxide, formate, and oxalate ions using a redox‐active phenazine‐based 2D covalent organic framework (Phen‐COF) and its phenazine monomer. Under similar irradiation conditions,Phen‐COFproduced 2.9 times more CO, 11 times more formate, and 13 times more oxalate compared to equimolar amounts of the monomeric phenazine, demonstrating that the COF architecture enhances catalytic performance (TOF COF : 10 −7 s −1 CO, 10 −8 s −1 formate, and 10 −11 s −1 oxalate). Structural analysis, including X‐ray diffraction and N₂ porosimetry, confirmed the COF's long‐range order and porosity. Mechanistic studies suggest a sequential formate‐to‐oxalate pathway, with CO and formate acting as intermediates. These results demonstrate the potential of the COF architecture to improve the performance of metal‐free, redox‐active aromatic systems such as phenazines to facilitate efficient and selective CO₂ conversion under mild conditions.

Chemistry↗

Effect of Carbon Dioxide Enrichment on Radish Production Using Nutrient Film Technique (NFT)

Radish plants (Raphanus sativus L. cvs. Cherry Belle, Giant White Globe, and Early Scarlet Globe) were grown in four different CO2 enriched environments, 0.04, 0.10, 0.50, and 1.00 kPa (400, 1000, 5000, 10000 ppm). Cultivar responses to CO2 treatments varied, where cv. Cherry Belle showed no significant response to CO2 enrichment, cv. Giant White Globe was moderately affected and Early Scarlet Globe was strongly affected. Enrichment at 0.10 kPa led to greater root dry matter (DM) than 1.00 kPa for cv. Giant White Glove, whereas 0.10 kPa produced greater storage root, shoot, and root DM than 1.00 kPa for cv. Early Scarlet Globe. The data suggest that 1.00 kPa CO2 may be detrimental to the growth of certain radish cultivars. Root:shoot ratios tended to increase with increasing CO2 concentration. Water use efficiency (g biomass/kg H2O) increased with increasing CO2 enrichment, up to 0.5 kPa but then declined at the 1.00 kPa treatment. The total nitric acid used to maintain nutrient solution pH was lowest at the 1.00 kPa treatment as well, suggesting a decreased demand of nutrients by the plants at the highest CO2 level.

Mackowiak, C. L.↗