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At least 109 records · Page 6

Chemical Modeling of the Capture of Radioiodine Species

Iodine is a common fission product resulting from the transmutation of uranium fuel in nuclear power reactors. The short-lived radioactive isotope, 131 I, with a half-life of around eight days, would be a particular health concern if released into the environment. Capture materials, such as activated carbon, are used routinely in nuclear power plants and medical isotope production facilities to remove this hazard during normal operations to reduce emissions to acceptable levels. Iodine, unlike other common fission products such as noble gases, is challenging because of the wide range of molecular forms and oxidation states (from +VII in IF 7 to -I in iodide) that it displays, which can interconvert both in the gas phase and in the solution phase for example. The work in this project is focused on three computational tasks. In the first, we consider the binding of iodine-containing molecules of varying oxidation states to the major component of activated carbon – pristine graphene-like sheets. The second task focused on molecular binding and possible chemical transformations resulting from the reaction of molecular iodine with chemical functional groups on the edge of the graphene sheets or surface defects in the sheet itself. The final task was associated with radiolytic breakdown of 131 I to 131 Xe in iodine containing molecules and investigated the resulting molecular fragmentation process both in the gas phase and on the graphene-like surface. For each of the tasks, the intent was to learn about the thermodynamics and kinetics of the chemical transformations and use the calculations to provide parameters for input into kinetic models describing these processes for interpretation of experimental data in future work.

07 ISOTOPE AND RADIATION SOURCES↗

Solid state NMR Investigation of Structural Differences in Pelletized DEB Samples

Upon hydrogenation of DEB pellets, which are composed of 75% virgin DEB and 25% of nanometer scale Pd catalysts on activated carbon, the uptake rate is strong, and the hydrogenation process is fast. However, the last batch of DEB pellets from KCNSC uptakes 10 times slower than traditional DEB pellets after ~ 50% consumption. In addition, the last batch of DEB getter pellets also became partially molten/wet during the hydrogenation process. This molten/wet phase during hydrogenation has only been observed with DPB and never with DEB formulation. DRIFT (diffuse reflection infrared Fourier transform) and XRD (x-ray diffraction) confirm that the questionable batch of DEB pellets from KCNSC are truly 100% DEB and not a mixture of DEB and DPB. So, there must be something different in the composition (like concentration and distribution of Pd) or interaction between the DEB molecules with the surrounding environment (activated carbon spreading medium). The possibility of some chemical contamination in the processing of this batch of questionable DEB getter pellets also comes to mind. Due to the ability of NMR to detect intermolecular interaction and sensitivity to small chemical concentration, NMR investigation was requested for this questionable batch of DEB getter pellets from KCNSC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoporous weakly coordinating anionic frameworks (Final Technical Report)

Under this award, we synthesized and characterized new weakly coordinating, anionic covalent organic frameworks. The motivation was to expand the class of covalent organic frameworks though the introduction of the first weakly coordinating anionic ones. The significance of the weakly coordinating anionic character of these frameworks is associated with the character of the counter (metal) cations in their pores. Those counter-cations, due to the inability to effectively coordinate to the pore walls, have a “naked”, and thus highly electrophilic, Lewis acidic character. Such properties are expected to translate to a number of interesting physical properties that can be potentially used for a range of energy-relevant applications. One of these applications is gas adsorption, separation, and storage. The electrophilic, Lewis acidic character of the counter-cations are expected to strongly bind to gas molecules entering the pores leading to higher gas sorption capacities. Other applications include heterogeneous catalysis, ion exchange, and solid state ion conduction. Within the project we explored a range of chemical blocks, and tested synthesis conditions to polymerize these building blocks to form the target materials. In particular, we focused on materials with group 15 elements like phosphorus in the oxidation state +5 and the coordination number 6, that have a formal -1 charge. The synthesis of such materials is challenging because its success depends on the absence of residual monomeric and oligomeric side-products in the pores, and the absence of significant framework interpenetration. Crystalline forms of these materials require sufficient reversibility of the polymerization reaction (which is difficult to achieve because group 15 elements like P tend to make strong covalent bonds with neighbored elements), as well as suitable polymerization rates that prevent the formation of kinetically controlled products. We had success with the preparation of anionic porous organic frameworks with anionic building blocks containing P(V)O6 octahedra synthesized through Yamamoto coupling reactions. These materials are non-crystalline because of the irreversible nature of the Yamamoto coupling reaction, but show porosity. The porosity and surface area can be significantly increased by co-reaction with electrostatically neutral co-reactants. Very high porosity and surface areas can be achieved when the materials are washed with hydrochloric acid. This method is commonly used to free products from Yamamoto coupling reactions from by-products. Indeed, this method removed by products from the pores of our materials, however it also led to the hydrolysis of the PO6 octahedra to form pending phosphonic acid groups (-PO3H)-groups in the frameworks (PA-POFs) which was actually not desired. Nonetheless, these materials showed high CO2 sorption capacities. In addition, they show extremely high (actually record) sorption capacities for the removal of a range of common micropollutants such as bisphenol A (BPA) and 4-nitrophenol in water. BPA is a wide-spread organic pollutant and a known endocrine disruptor. The maximum adsorption capacity of BPA at equilibrium is found to be as high as 3,366 mg g-1 by Langmuir adsorption model, which is more than 10 times greater than peer materials. The polymer also rapidly removes various other organic micropollutants with more than 90% removal efficiencies. In addition, the PA-POF material can be regenerated at least five times by mild washing using methanol without significant loss in removal efficiency. This is significant advantage over commonly used activated carbon materials (that are in Brita water faucet filters, for example). Comparison studies showed that only materials with the phosphonate groups show extreme sorption although the number of PA group is actually small according to solid state NMR and EDX data. More research would be needed to investigate why this is (a possibility is that the phosphonate groups have a multiplying effect in which a PA-induced initial adsorption leads to the adsorption of much more adsorbate). The extreme sorption capabilities can also be visually seen when colored adsorbates such as 4-nitrophenol are used, as the adsorption of the nitrobenzene leads to the decoloration of the solution. We have produced three short videos that illustrate the sorption capabilities compared to two peer materials (activated carbon from dismantled Brita water filters, and a electrostatically neutral, chemically related, porous organic polymer, respectively).

36 MATERIALS SCIENCE↗

Data for 3-Hydroxypropionic Acid Recovery from Fermentation Broth through Novel Downstream Processing: Technoeconomic Analysis

This study develops and validates a simplified, fully solvent-free downstream processing (DSP) strategy for high-purity recovery of 3-hydroxypropionic acid (3-HP) from real fermentation broth containing 62.3 g/L of 3-HP. Optimized activated carbon treatment achieved 98% color removal, while Amberlite IRA-67 was operated at pH 4.5 and 30 °C to minimize product loss. This is the first integrated demonstration of a fully solvent-free DSP enabling recovery of bio-based 3-HP as both a solid sodium salt and a concentrated aqueous solution, supported by techno-economic analysis. At lab scale, the process achieved 77.3% recovery of sodium 3-HP with 83.2% (w/w) purity and produced a 30% (w/v) aqueous solution. Techno-economic analysis yielded minimum selling prices of $0.551/kg for the solution and $0.892/kg for the salt, both below target thresholds for cost-competitive bio-acrylic acid production. Overall, these results demonstrate an efficient, scalable, and economically viable industrial pathway for 3-HP recovery.

Bioproducts↗

Techno-Economic Analysis and Life Cycle Assessment of Waste Lignin Fractionation and Valorization Using the ALPHA Process

Techno-Economic Analysis (TEA) and Life Cycle Assessment (LCA) were performed on the Aqueous Lignin Purification with Hot Agents (ALPHA) process, which is being investigated for the fractionation and purification of raw, bulk lignins recovered from cellulosic ethanol biorefineries or Kraft pulp mills. Here, ALPHA is proposed for the isolation of lignin from a corn stover-to-ethanol plant into purified low, medium, and high molecular weight (MW) fractions for producing polyurethane foam, activated carbon, and carbon fiber, respectively. A scenario analysis was conducted to determine the effect of ALPHA solvent choice on process economics and environmental performance. Solvent choice was found to have a significant impact on ALPHA, with a minimum selling price of 838/tonne with use of acetic acid vs 463/tonne with ethanol. Conversion of the lignin, processed with ethanol solvent, to high-value products yields 151 million/year in profit, which over 30 years results in a total net present value of 533 million. A life cycle assessment was conducted to determine the “gate-to-gate” greenhouse gas emissions and energy consumption of the lignin-based products compared to fossil-based equivalents. In conclusion, a value allocation scenario was conducted and it was determined that products generated using the ALPHA process with ethanol have similar or lower greenhouse gas emissions than the same products from fossil feedstocks.

09 BIOMASS FUELS↗

Recovery of Oxpure 612C-50 Coconut Carbon Particles Using Bump Arrays

Cyanide is used to leach gold from crushed ore (solid matrix) into a gold cyanide solution. The gold is extracted from the cyanide solution by adsorption onto activated carbon. The gold extraction process occurs when the activated coconut carbon is placed into tanks that contain the gold cyanide solution either in a batch process or into a continuous flow circuit. The coconut carbon is then removed from the solution for gold recovery. The use of the mesofluidic separation system (a deterministic lateral displacement system) can significantly reduce costs and waste generated from the process of removing the coconut carbon from the solution. In the coconut carbon recovery process used at many gold mines in Nevada, the gold is attached to carbon particles that are still in the cyanide liquor. The mesofluidic system can rapidly remove the gold bearing carbon particles from the cyanide liquor quickly and with no operating costs. The benefits include: • Reduce operational costs related to filtration and hydro-cyclones • Reduced acid usage for the elution gold stripping phase as only 25% of the fluids will follow the carbon particles to the final express lane when two mesofluidic systems are used in series This alternative particle removal techniques would be advantageous. A promising technique for removing larger particles from slurries is mesofluidic separation, similar to deterministic lateral displacement arrays or “bump” arrays [1] but operates at much larger flow rates. As described by Pease, et al. [2], “Bump arrays in deterministic lateral displacement devices separate large particles from small particles using arrays of staggered posts. Large particles, defined as those with radii larger than the distance between the edge of a post and the stagnation streamline from the next downstream post, must bump toward one side of the device, whereas particles smaller than this distance slalom from entrance to exit without net lateral displacement.” Unlike filters or sieves, the posts in the arrays that cause separation do not block or occlude particle flow but work because particles go around the posts. Unlike hydrocyclones separation, separation is not driven by particle density, because gravitational forces are unimportant to mesofluidic separation. Burns, et al., and Pease, et al., have shown that particles may be separated from complex suspensions, under turbulent flow conditions, and at industrially important flow rates [3-5]. They have also recently shown that mesofluidic devices may be arranged in series to increase separation performance [6]. In this paper, we evaluate the mesofluidic system for the separation of commercial OxPure GR 612 Charred Coconut shell particles as a proof of principle test for the rapid separation using the 1500 micron cut mesofluidic separator. We first describe the experimental system and conditions. We then present the experimental results. [1] Huang, L.R., E.C. Cox, R.H. Austin, J.C. Sturm. 2004. Continuous particle separation through deterministic lateral displacement. Science, 304, 987–990. https://doi.org/10.1126/science.1094567. [2] Pease L.F., J.A. Bamberger, C.A. Burns, and M.J. Minette. 2021. Large Particle Separation from Non-Newtonian Slurries using Bump Arrays. In Proceedings of the ASME 2021 Fluids Engineering Division Summer Meeting FEDSM2021-65904, V003T08A023. New York, New York: ASME. doi:10.1115/FEDSM2021-65904 [3] Burns C.A., T.G. Veldman, J. Serkowski, R.C. Daniel, X.-Y. Yu, M.J. Minette, L.F. Pease. 2021. Mesofluidic separation versus dead-end filtration. Separation and Purification Technology, 254, 117256. https://doi.org/10.1016/j.seppur.2020.117256. [4] Pease L.F., J.E. Serkowski, T.G. Veldman, J. Williams, X.-Y. Yu, M.J. Minette, J.A. Bamberger, C.A. Burns. 2021. Can Bump Arrays Separate Particles from Turbulent Flows?. In Proceedings of the ASME 2021 Fluids Engineering Division Summer Meeting FEDSM2021-67696, V003T08A024. New York, New York: ASME. doi:10.11

mesofluidic separation, slurry, bump array↗

The status and prospects of materials for carbon capture technologies

In order to combat climate change, carbon dioxide (CO 2 ) emissions from industry, transportation, buildings, and other sources need to be captured and long-term stored. Decarbonization of these sources requires special types of materials that have high affinities for CO 2 . Potassium hydroxide is a benchmark aqueous sorbent that reacts with CO 2 to convert it into K 2 CO 3 and subsequently precipitated as CaCO 3 . Another class of carbon capture materials is solid sorbents that are usually functionalized with amines or have natural affinities for CO 2 . The next wave of materials for carbon capture under investigation includes activated carbon, metal–organic frameworks, zeolites, carbon nanotubes, and ionic liquids. In this issue of MRS Bulletin, some of these materials are highlighted, including solvents and sorbents, membranes, ionic liquids, and hydrides. Other materials that can capture CO2 from low concentrations of gas streams, such as air (direct air capture) are also discussed. Also covered in this issue are machine learning-based computer algorithms developed with the goal to speed up the progress of carbon capture materials development, and to design advanced materials with high CO 2 capacity, improved capture and release kinetics, and improved cyclic durability.

36 MATERIALS SCIENCE↗

Electron beam treatment for the removal of 1,4-dioxane in water and wastewater

Electron beam (e-beam) treatment uses accelerated electrons to form oxidizing and reducing radicals when applied to water without the use of external chemicals. In this study, electron beam treatment was used to degrade 1,4-dioxane in several water matrices. Removal improved in the progressively cleaner water matrices and removals as high as 94% to 99% were observed at a dose of 2.3 kGy in secondary effluent. 1,4-dioxane removal was confirmed to be primarily through hydroxyl radical oxidation. The calculated electrical energy per order was found to be 0.53, 0.26, and 0.08 kWh/m 3 /order for secondary effluent (Avg. total organic carbon (TOC) 9.25 mg/L), granular activated carbon effluent (TOC 3.46 mg/L), and ultrapure water, respectively, with a 70% generation and transfer efficiency applied.

1,4-dioxane↗

Tailored mesoporous structures of lignin-derived nano-carbons for multiple applications

This work uses a one-step KOH activation for lignin precursors to produce ultra-high mesoporous activated carbons (ACs) with an unprecedented combination of the surface area of 3207 m 2 g -1 and mesopore ratio of 76%. The ACs are applied for supercapacitors (SCs) and methylene blue (MB) adsorption. The capacitance of the SCs in the three-electrode system reaches 812.3 F g -1 and demonstrates a remarkable maximum MB adsorption capacity of 1250 mg g -1 . By modifying the process conditions, the mesopore ratio of ACs could be controlled from 10% to 80%. Compared with one-step activation, a two-step method produced microporous carbons with a lower surface area of 1227 m 2 g -1 and a high micropore ratio of 73%. The capacitance of SCs with two-step ACs reached 228.1 F g -1 and the maximum adsorption capacity of 476.19 mg g -1 for MB adsorption. The two-step method limited the surface area but had a higher oxygen surface functionality, benefiting its electrochemical performance. A techno-economic analysis reveals that the one-step KOH activation-based process develops ACs with a minimum selling price of $7648/ton. In conclusion, this work demonstrates tuning the processing-structure-property-performance relationship of lignin-based ACs to make an economically viable domestic carbon source.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Validation of neutron-induced reactions on natural carbon using an active target at neutron energies up to 22 MeV at LANSCE

A single crystal chemical vapor deposited (sCVD) diamond detector is used as an active target to measure neutron-induced reactions on natural carbon using the neutrons produced by spallation, with a broad energy spectrum at LANSCE. Additionally, the neutron-induced reactions are detected in the diamond as low as E n = 400 keV and up to approximately 100 MeV. Relative cross sections for C 12 ( n , α 0 ) , C 12 ( n , p 0 ) , C 12 ( n , d 0 + p 1 ) , and C 13 ( n , α 0 ) are reported up to E n = 22 MeV and comparisons on detected pulse-height spectra and detector response of scattering reactions are made with GEANT4 simulations using the ENDF/B-VIII.0 evaluated nuclear data library up to 20 MeV. The results are compared with past experimental data, including other works that incorporate diamond detectors as an active carbon target. In addition, R-matrix calculations for the C 13 + n system are presented.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗

Methane Remediation using Biocatalysts in Gas-Solid Reactor – Challenges and Prospects

One of the engineering grand challenges of the 21 st century is to develop carbon sequestration methods due to human activities. Carbon dioxide and methane are the two most abundant greenhouse gases with methane having a higher global warming potential (GWP) than carbon dioxide. Methanotrophs are a time of bacteria that consumes methane and can produce different kinds of organic acids. Wild methanotrophs produce a range of products and can be specifically selected and genetically engineered to produce a specific product. Improvement of bioreactor design for a solid-gas mass transfer is necessary for this technology to move forward. Poor solubility of methane requires high energy input for the conversion of methane. This paper reviews some relevant technology in bioreactor design of gas and liquid/solid interfaces and describes the scope of the project here at LLNL and the objectives it seeks to achieve in the geometric design of reactor of methanotroph.

36 MATERIALS SCIENCE↗

M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗

Preprocessing of municipal solid waste towards thermal insulating material

Municipal solid waste (MSW) is one of the significant challenges in today’s world. A continuous surge in population, increasing living standards, and rapid urbanization are generating an enormous quantity of MSW. For example, the Environmental Protection Agency (EPA) reported that the total generation of MSW in the United States in 2018 was 292.4 million tons. Improper management of this MSW often leads to the release of greenhouse gases, emission of particulate matters, and formation of dioxins, which all ultimately contributes to climate change. Recycling these wastes via landfills with gas recovery and/or energy and material production via thermal and chemical conversions could be viable options to manage these challenges. Depending on the inherent chemical and structural properties of unrecycled wastes, the carbon structures can be tailored for processing and reuse in manufacturing of structural composites, building materials such as insulation, carbon dense reactant materials such as activated carbon, and so on. According to the EPA’s estimation, MSW in the United States is approximately 23% paper and paperboard, 12% plastics, 6% wood and 6% is textiles. Thus, this research focused on the feasibility of using the MSW as insulation material for the construction sector. The goal of this work was to determine the range of particle sizes, consolidation ratios, and component blends that can achieve insulation R-values within at least 70% that of traditional blown cellulose fiber. To achieve this goal, we designed the testing matrix based on five different component blends, three different particle sizes, and three different compaction level. An American Society for Testing and Materials (ASTM) method (C-739) was used to measure the R-value of the insulation material. Results showed that, adding more paper component in addition to smaller particle size and loose compaction made the insulation similar to the traditional blown cellulose fiber insulation as the R-value was within a range of 2.5-3.0 per inch.

42 ENGINEERING↗

M2CT-22IN1202096 Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy-rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling in the AspenOne Suite will be used to determine each component’s sensitivities, costs, inputs, and outputs. Dispatch modeling in the FORCE toolset will optimize the entire system and calculate the NPV for the refinery lifetime. Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗

Design for Carbon Conversion Product Pathways with Nuclear Power Plant Integration (PCC)

Coal is a globally abundant resource that historically has been used for power generation via combustion. As the power industry replaces coal with cleaner methods of generation, energy rich coal could be used in other chemical and fuel applications. This study presents a coal utilization option in which coal combustion is replaced with a carbon-free nuclear power plant and the coal is upgraded to valuable products for a variety of markets. Coal is prepared for conversion first by the pyrolysis process, which will optimize solid, liquid, and gaseous products based on the market size and potential product value, maximizing the monetary value of coal. This process is designed using bituminous coal from the Appalachian region as a basis to provide a pathway to preserve or transition coal-related jobs and create new jobs associated with the clean energy transition. Process modeling will be used to determine each component’s sensitivities, costs, inputs, and outputs Advanced and light-water reactors are considerations to supply the heat, steam, and electricity to the process. This paper focuses on the technical and market analysis used to determine the optimal processes and product pathways for the carbon refinery. Product pathways are on activated carbon, formic acid synthesis, and methanol synthesis for further upgrading to marketable chemical and polymer products.

01 COAL, LIGNITE, AND PEAT↗