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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Iron Oxide Reduction Rate Affects Iron Product Morphology

Magnetite concentrates from different parts of the Mesabi Range, exhibiting varying tendencies to encapsulate, were reduced using thermogravimetric analysis (TGA) and a high-temperature confocal scanning laser microscope (CSLM). Gas-phase mass-transfer conditions were intentionally varied by employing two reactors with different geometries: the TGA produced significantly slower reduction, whereas the CSLM setup yielded reduction rates up to 20 times faster under mass-transfer-controlled conditions. A preliminary mechanism is proposed to explain the transition from a porous iron product to a dense encapsulating layer. Encapsulation is interpreted as the outcome of competition between pore creation, driven by the reduction rate, and pore elimination, driven by surface diffusion. When pore formation is insufficient to counteract pore coarsening, a dense iron layer develops and restricts further reduction.

encapsulation↗

Dissolution of Fluoride Salts in Hanford Tank Waste

The Direct Feed High-Level Waste (DFHLW) strategy seeks to bypass the Hanford Waste Treatment and Immobilization Plant Pretreatment Facility while retaining some processing functions to maximize waste feed loading and minimize high-level waste (HLW) waste volume. The DFHLW flowsheet needs leaching, washing, and solids concentration operations either in new or existing tanks. The effectiveness and efficiency of sludge washing has a substantial impact on DST space, mission duration, and the evaporation and low-activity waste (LAW) treatment operations required by these large wash-water additions. One target species requiring washing is fluoride. The HLW glass composition limits for fluorine drive operations to dissolve fluoride-bearing salts into the LAW fraction and thereby maximize waste loading in HLW glass. The fluoride in many high-level wastes at Hanford is predominantly in the form of fluoride-salt precipitates: villiaumite (NaF), kogarkoite (Na 3 FSO 4 ), and natrophosphate (Na 7 F(PO 4 ) 2 ·19H 2 O). Fluoride produces melter off-gas that creates corrosion risk in the off-gas system piping, while the sulfate and phosphate in the fluoride double salts kogarkoite and natrophosphate can be detrimental to glass waste loading. Fluoride salts are sparingly soluble, with solubilities ranging from approximately 40 to 130 kg per kL of pure water, and the dissolution kinetics of the three fluoride salts are not well known. Unexpected delays in a tank dissolution process could be encountered as a result of the lack of information about dissolution rates. In addition, if the double salts show transient non-stoichiometric dissolution of fluoride versus phosphate or sulfate, unexpectedly high concentrations of one of these other constituents could be produced. Washington River Protection Solutions authorized Pacific Northwest National Laboratory to collect the available data for fluoride salt dissolution rate, provide a scoping estimate of dissolution time if possible, and identify gaps in the understanding and predictive capability for estimating dissolution time. Open literature and Hanford reports were reviewed to document, understand, and (where possible) evaluate limitations on fluoride salt equilibria and dissolution kinetics, including both mass transport and surface reaction rate. Scoping estimates of dissolution time were made for mass-transfer-controlled dissolution of spherical particles of fluoride salts suspended in liquid. This is not the only potential governing mechanism; dissolution could be substantially slower if the surface reaction rate (the rate of release of ions from the surface) is the controlling mechanism. When the minimum amount of water for complete dissolution is used and the slip velocity between the liquid and suspended particles is less than or equal to the terminal settling velocity, the estimated mass-transfer rates allow 0.1 mm particles of fluoride salt to dissolve in minutes at 25 °C in water containing no other dissolved salts. Much larger solids, such as the 6-mm chunks that have been seen in heels, could take a few hours to more than a week to dissolve. The actual dissolution times will depend strongly on the actual slip velocity, the extent of particle suspension, constraint by surface reaction rates, the ratio of solvent to solid, and the presence of common ions that shift the solubility equilibria to restrict dissolution of fluoride salts.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Magmatic, hydrothermal and ore element transfer processes of the southeastern Archean Superior Province implied from electrical resistivity structure

Although magmatic- and metamorphic- derived fluids are widely recognized mineralizing agents, the role of crustal architecture in defining source and sink zones within the middle to lower crust and upper mantle of ancient orogens remains enigmatic. The globally largest and best-preserved Archean greenstone belts lie in the Superior Province, Canada. They provide an ideal location to investigate the influence of igneous construction and subsequent syn-deformational plutonism and metamorphism on the localization of metal-rich melts and fluids throughout the crustal column. Integration of three-dimensional magnetotelluric modelling and seismic reflection sections across the Abitibi subprovince reveals details of a 'whole-of-crust' magmatic and hydrothermal system. East-west low resistivity structures broadly underlie the surface traces of the major deformation zones that are host to significant gold endowment (>200 Moz), while mid-crustal cross trends suggest mineralized fluids flowed along 'pipes' within fault planes. Most low resistivity structures are inferred to represent domains containing interconnected zones of graphite and/or sulfide. Furthermore, these delineate relict mantle source/transit domains and crustal pathways enriched by the flow of magmas or metamorphic fluids genetically related to a late-stage pulse of ore-bearing magmatism, possibly as a result of slab break-off or delamination. Using the combined MT and seismic data, we develop a 3-D crustal-scale model which highlights how evolving orogenic architecture-controlled mass transfer and metallogenic processes developed.

58 GEOSCIENCES↗

Correlation Between Microscopic Current Fluctuations Observed at Ultra-Microelectrodes and Macroscopic Bulk Electrolysis Performance in Redox-Active Microemulsions

Microemulsions (μEs) have been proposed as redox flow battery (RFB) electrolytes that maximize ionic conductivity and charge capacity by synergizing two immiscible phases. However, charge transfer during electrolysis in μEs is poorly understood. Here, we show that ultramicroelectrode electrolysis of ferrocene-loaded μEs –20%, 60%, and 90% water - reveals stochastic current fluctuations. These are differentiated in the scanning electrochemical microscopy (SECM) geometry, where power spectral density analysis showed distinct changes in the frequency contributions. SECM in the substrate generation-tip collection mode showed that fluctuations arise under mass-transfer control. Significant differences in the diffusion coefficient of ferrocene species were deducted from SECM approach curves, suggesting phase transfer behavior. Using bulk electrolysis, we calculated the charge accessibility and cycling behavior in the μEs. A decrease in the stochastic behavior of the μEs seems to correlate to a higher accessibility and cycling performance, with the 90% water μE displaying the best reversibility and the 60% the lowest. Altogether, these results suggest that Marangoni-type convection driven by concentration gradients and/or μE restructuring during charge transfer play a role in the electrochemical performance of μEs. This presents opportunities for screening and diagnosing the performance of these emerging RFB electrolytes.

25 ENERGY STORAGE↗

Reaction Temperature Manipulation as a Process Intensification Approach for CO 2 Absorption

Reactor temperature manipulation to increase product yields of chemical reactions is a known technique used in many industrial processes. In the case of exothermic chemical reactions, the well-known Le Chatelier’s principle predicts that a decrease in temperature will displace the chemical reaction toward the formation of products by increasing the value of the equilibrium constant. The reverse is true for endothermic reactions. Reactor temperature manipulation in an industrial system, however, affects the values of many variables, including physical properties, transport parameters, reaction kinetic parameters, etc. In the case of reactive absorption, some variables change with increasing temperatures due to solute absorption, while others change in such a way that the solute absorption rate decreases. For example, temperature drop increases product formation for exothermic reactions but reduces the value of transport parameters, leading to decreasing interfacial concentrations and absorption rates. Therefore, temperature manipulation strategies must be designed carefully to achieve the process goals. In this work, we theoretically study the use of temperature as a tool to increase CO 2 absorption by solvents in a semi-batch reactor. A computer code has been developed and validated using reported experimental data. Calculated results demonstrate an increase in absorbed CO 2 of more than 28% with respect to the highest temperature used. Despite high agitation and high gas flow rate, the system is mass transfer controlled at short times, becoming kinetically controlled as time increases. An operating strategy to decrease cooling energy costs is also proposed. This study reveals that reactor temperature manipulation can be an effective process to improve CO 2 absorption by solvents in two-phase semi-batch reactors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A mathematical analysis of carbon fixing materials that grow, reinforce, and self-heal from atmospheric carbon dioxide

Carbon fixing materials are a new class of self-healing, self-reinforcing materials we have introduced that utilize ambient CO 2 to chemically add to an ever extending carbon backbone. This class of materials can utilize biological or non-biological photocatalysts and support a wide range of potential backbone chemistries. However, there is no analysis to date that describes their fundamental limits in terms of chemical kinetics and mass transfer. In this computational study, we employ a reaction engineering, and materials science analysis to answer basic questions about the maximum growth rate, photocatalytic requirements and limits of applicable materials. Our proposed mathematical framework envelops three main functions required for carbon fixing materials: (1) adsorption of CO 2 from air, (2) photocatalytic reduction of CO 2 into selected monomers, and (3) polymerization of CO 2 -derived monomers. First, by performing a Damköhler number analysis, we derive criteria for the cross over from kinetic control to mass transfer limited growth, setting upper limits on performance of a potential photocatalyst. Next, we analyze photocatalytic reduction of CO 2 to single carbon products, using known catalytic pathways and kinetic data. We identify formaldehyde as a C1 intermediate having unique potential for incorporation into the material backbone of carbon fixing materials. As an example, we find that a diamond-shaped reaction network graph for CO 2 reduction, passing through CO and HCOOH intermediates, accurately describes kinetic data for cobalt-promoted TiO 2 nanoparticles at room temperature and 1 atm CO 2 . Finally, as an applied case study, we consider and analyze the example of a carbon fixing poly(oxymethylene) system with embedded catalyst promoting the photocatalytic reduction of CO 2 to formaldehyde. The latter then trimerizes to a trioxane monomer which subsequently polymerizes to polyoxymethylene. This reaction engineering analysis introduces benchmarks for carbon fixing materials with respect to achievable rates of photocatalysis, adsorption, and polymerization. These results should prove valuable for the design, evaluation, and benchmarking of this emergent and new class of environmentally sustainable materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Performance of sweeping gas membrane distillation for treating produced water: Modeling and experiments

Membrane distillation (MD) has shown promise for desalination of produced water (PW), but there are very few studies reported on the performance of MD with real PW and the characteristics of the fouling and scaling in MD. Among different MD configurations, sweeping gas MD (SGMD) is the least studied configuration. Here we report the application of SGMD for treating high-salinity PW (123 g L -1 ). The SGMD operating conditions were first carefully optimized through pure water MD experiments by varying operating conditions. The flux evaluation was accompanied by a detailed Aspen Custom Modeler simulation based on the electrolyte-NRTL thermodynamic model to better understand the heat and mass transfer in the feed and permeate channel. Supported by experiments, modeling results confirmed the partial condensation of the vapor in the permeate channel. Furthermore, it was concluded that the saturation of the sweeping gas is controlling the overall mass transfer through the membrane. Selected membranes and optimized conditions were then used to conduct short-term and long-term performance tests with PW. In long-term MD test, the concentration of the PW increased by a factor of two (50% water recovery), while the membrane exhibited small flux decline. Elemental analysis showed that strontium and sodium were the major scalant compounds.

42 ENGINEERING↗

Intrinsic kinetics of water-inhibited ultra-lean methane oxidation over PtPd-Mg/ θ -Al 2 O 3 catalyst

Here, this study develops intrinsic methane oxidation kinetics for ultra-lean methane conditions in the presence of water over a highly active and stable PtPd–Mg/θ-Al 2 O 3 catalyst. Comprehensive laboratory experiments were conducted over a wide range of methane concentrations (150–1200 ppm CH 4 ), water contents (1–5% H 2 O), and industrially relevant space velocities (80,000 ≤ GHSV ≤ 160,000 h -1 ). These systematic experiments informed a two-dimensional, axisymmetric, multiscale reactor model that was used to develop and validate methane oxidation kinetics under practically relevant conditions, including non-isothermal operation and high conversion regimes. Combined experimental and modeling results revealed significant intraparticle diffusion resistance and transport-induced reaction exotherm at elevated temperatures, which limited catalyst utilization despite high intrinsic activity. These transport effects were explicitly incorporated into the reactor model, enabling accurate estimation of intrinsic kinetic parameters without reliance on conventional effectiveness-factor corrections. The resulting kinetic model successfully captured both kinetically controlled and mass-transfer-limited regimes and reliably predicted CH 4 conversion across broad ranges of temperature, methane concentration, and water content

Heat and mass transfer limitations↗

Electrochemical Manipulation and Radiolytic Evaluation of Organic Phase Neptunium

Presentation for Seed LDRD proposal presentation: This Seed LDRD research proposes to test an innovative approach to precisely control the oxidation state distribution of neptunium (Np) under used nuclear fuel (UNF) reprocessing conditions using novel electrochemical methods. Current UNF reprocessing technologies are not financially viable in the US, requiring significant scientific and technological innovation to improve cost efficiency. Reducing the number of process cycles is one avenue for increasing cost efficiency, of which resolving the challenge associated with isolating Np is critical. Under envisioned process conditions, Np is present in a mixture of extractable (Np(IV) and Np(VI)) and inextractable (Np(V)) oxidation states, the distribution of which is dependent on several factors, including ionizing radiation dose, that change throughout a reprocessing scheme. Consequently, Np unintentionally partitions into various UNF reprocessing phases and product streams, ultimately increasing the number of process cycles to isolate UNF components. Here, we propose to employ novel, high surface area, optically transparent, Ligand Modified tin-doped indium oxide Electrodes (LMES). These LMEs bind Np, and therefore enable concurrent generation and spectroscopic characterization of Np oxidation states in organic solutions. These proof-of-concept experiments will: (i) facilitate optimization of the proposed electrochemical system conditions for Np oxidation state manipulation; (ii) identify the accessible electrochemical window for Np complexes in the organic phase; (iii) report characteristic optical spectra for each accessible complexed Np oxidation state; and (iv) determine the lifetime and partitioning of a given atypical Np oxidation state in the organic phase in the presence and absence of ionizing radiation fields. The data gathered by this Seed LDRD will provide support for the design of an electrochemical process concept for the precise manipulation of Np oxidation states in UNF reprocessing solvent systems, with the intention of providing advanced control over Np mass transfer, and thus greater process efficiency and economy.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Smart Droplets Stabilized by Designer Surfactants: From Biomimicry to Active Motion to Materials Healing

The science and technologies of emulsion droplets have been a long‐term focus of extensive research endeavors for their practical utility across a breadth of industries, including pharmaceutical products, oil recovery processes, and the food sciences. However, with advances in materials chemistry and characterization tools, new emerging areas are arising with a focus on “smart droplets”. The versatility of emulsion droplets across is based on their ability to partition and create isolated systems with properties defined by the liquid–liquid interface, while preparative routes allow manipulation of droplet size, stability, and encapsulated contents. As described in this article, significant efforts are being devoted to creating new types of droplets by “activating” this interface through the incorporation of reactive structures that trigger droplet response to applied or environmental stimuli (e.g., pH, temperature, salt, or external fields). Moreover, parallels between droplets and live cells inspire efforts to conceive systems that resemble biological motifs or that can produce cellular behaviors that imitate biology (e.g., swarming, communication, or motion). Here, the authors highlight recent advances in smart droplets, with emphasis on organic, polymer, and/or particle surfactants that give rise to inter‐droplet communication (via aggregation, fusion, division, or mass transfer), droplet vehicles for controlled delivery, autonomous droplet motion, and tunable emulsion inversion. Especially emphasized is the macromolecular design to produce reactive and functional surfactants, which are crucial to responsive droplet behavior and their underlying mechanisms. More generally, the exquisite interplay between materials science and biology inspires the review of this research area that provides unique opportunities for insight and inspiration into the capabilities of new droplet designs.

36 MATERIALS SCIENCE↗

Biopolymer-supramolecular polymer hybrids for photocatalytic hydrogen production

Solar generation of H 2 is a promising strategy for dense energy storage. Supramolecular polymers composed of chromophore amphiphile monomers containing perylene monoimide (PMI) have been reported as crystalline light-harvesting assemblies for aqueous H 2 -evolving catalysts. Gelation of these supramolecular polymers with multivalent ions creates hydrogels with high diffusivity but insufficient mechanical stability and catalyst retention for reusability. We report here on using sodium alginate (SA) biopolymer to both induce supramolecular polymerization of PMI and co-immobilize them with catalysts in a robust hydrogel with high diffusivity that can also be 3D-printed. Faster mass transfer was achieved by controlling the material macrostructure by reducing gel diameter and microstructure by reducing biopolymer loading. Optimized gels produce H 2 at rates rivaling solution-based PMI and generate H 2 for up to 6 days. The PMI assemblies in the SA matrix create a percolation network capable of bulk-electron transfer under illumination. These PMI–SA materials were then 3D-printed on conductive substrates to create 3D hydrogel photoelectrodes with optimized porosity. The design of these versatile hybrid materials was bioinspired by the soft matter environment of natural photosynthetic systems and opens the opportunity to carry out light-to-fuel conversion within soft matter with arbitrary shapes and particular local environments.

36 MATERIALS SCIENCE↗

Coupling Subsurface and Above-Surface Models for Optimizing the Design of Borefields and District Heating and Cooling Systems

Accurate dynamic energy simulation is important for the design and sizing of district heating and cooling systems with geothermal heat exchange for seasonal energy storage. Current modeling approaches in building and district energy simulation tools typically consider heat conduction through the ground between boreholes without flowing groundwater. While detailed simulation tools for subsurface heat and mass transfer exist, these fall short in simulating above-surface energy systems. To support the design and operation of such systems, the study developed a coupled model including a software package for building and district energy simulation, and software for detailed heat and mass transfer in the subsurface. For the first, it uses the open-source Modelica Buildings Library, which includes dynamic simulation models for building and district energy and control systems. For the heat and mass transfer in the soil, it uses the TOUGH simulator. The TOUGH family of codes can model heat and multi-phase, multi-component mass transport for a variety of fluid systems, as well as chemical reactions, in fractured porous media. The study validated the coupled modeling approach by comparing the simulation results with one from the g-function based ground response model. It then looked into effects when the water table and the regional groundwater flow are considered in the ground, from the perspective of heat exchange between borehole and ground, and the electrical consumption of the district heating and cooling systems. To access the simulation models, please find the links in the submission: -- For coupled approach validation: see model Buildings.Fluid.Geothermal.Borefields.Examples.BorefieldsWithTough and Buildings.Examples.DistrictReservoirNetworks.Examples.Reservoir3Variable_TOUGH from the "Modelica Building Library" resource, branch issue1495_tough_interface, commit a2667c0. -- For the study of the effect of water table: see model Buildings.Examples.DistrictReservoirNetworks.Examples.Reservoir3Variable_TOUGH from he "Modelica Building Library" resource, branch issue1495_tough_interface_moreIO, commit 760de49. -- For the study of the effect of regional groundwater flow: see Buildings.Examples.DistrictReservoirNetworks.Examples.Reservoir3Variable_TOUGH from he "Modelica Building Library" resource, branch issue1495_tough_interface_moreIO_3D, commit c2a2d2a. The coupling interface script "GrounResponse.py" can be found from the above links in the folder Buildings/Resources/Python-Sources. Also, the needed files for TOUGH simulation are in the folder Buildings/Resources/Python-Sources/ToughFiles that can be accessed through the above links. A brief description of these files is given below; detailed specifications for the first three files may be found in the TOUGH3 Users Guide (Jung et al., 2018) https://tough.lbl.gov/documentation/tough-manuals/. (1) INCON - initial conditions for each grid block (2) INFILE - main input file with material properties and control parameters (3) MESH - description of the computational grid (4) readsave - Modelica/TOUGH interface program: read the final output of TOUGH simulation after TOUGH time step and prepare for transfer to Modelica for next Modelica time step (5) readsave.inp - input parameters for program readsave (6) writeincon - Modelica/TOUGH interface program: write the output of Modelica after Modelica time step and prepare for transfer to TOUGH as initial conditions for the next TOUGH step (7) writeincon.inp - input parameters for program writeincon

15 GEOTHERMAL ENERGY↗

Coupling subsurface and above-surface models for optimizing the design of borefields and district heating and cooling systems in the presence of varying water-table depth. In: Proceedings, 46th Workshop on Geothermal Reservoir Engineering

Dynamic energy simulation is important for the design and sizing of district heating and cooling systems with geothermal heat exchange. Current modeling approaches in building and district energy simulation tools typically consider heat conduction through the ground between boreholes, without flow of groundwater. On the other hand, detailed simulation tools for subsurface heat and mass transfer exist, but these fall short in simulating above-surface energy systems. To support the design and operation of such systems, we have developed a coupled model including a software package for building and district energy simulation, and software for detailed heat and mass transfer in the ground. For the first, we use the open-source Modelica Buildings Library, which includes dynamic simulation models for building and district energy and control systems. For the heat and mass transfer in the soil, we use the TOUGH simulator. TOUGH can model heat and multi-phase, multi-component mass transport for a variety of fluid systems, as well as chemical reactions, in fractured porous media. In previous work, we described the coupling of these software packages, including how time-dependent boundary conditions for the borehole walls are synchronized for use in Modelica and TOUGH. We verified that the coupled Modelica/TOUGH code produced consistent results with the original Modelica code for an idealized problem in which heat transfer was purely by conduction in a uniform geologic medium. Here, we examine less idealized problems for which TOUGH’s advanced capabilities for modeling fluid flow are required. The first problem has a shallow vadose zone, and the second problem has a thicker vadose zone with a water-table depth that varies in time, which requires a fine vertical grid discretization for the TOUGH model.

Doughtry, Christine↗

Fracture Characterization Via AI‐Assisted Analysis of Temperature Logs

Abstract Fractures control fluid flow, mass transport, and heat transfer in a geothermal reservoir. This makes accurate characterization of fracture networks a prerequisite for optimal design and control of a reservoir's exploitation. We develop a deep‐learning procedure to identify fracture locations via interpretation of temporally and spatially continuous downhole temperature measurements. A long short‐term memory fully convolutional network (LSTM‐FCN) is used both to capture long‐term dependencies in sequential temperature data and to distill local features around fractures. A wellbore and fractured‐reservoir thermal model is established to generate temperature data for network training. The trained LSTM‐FCN exhibits a unique ability to detect multiple fractures intersecting a borehole. We use the LSTM‐FCN algorithm to evaluate the effectiveness of different‐stage wellbore temperature measurements on fracture detection in a complex fractured system. Our experiments reveal that the use of various‐stage temperature information as an input feature set improves the robustness of fracture detection to noise interference. This study indicates the practical feasibility of obtaining accurate fracture‐network reconstructions from temperature signals, at reasonable computational cost.

Yang, Xiaoyu↗

Flexible cryogenic air separation unit—An application for low-carbon fossil-fuel plants

In this study, the rapid integration of intermittent renewable sources into the electricity grid is driving the need for a flexible cryogenic air separation unit (ASU) coupled with a low-carbon fossil-fuel plant. However, the state-of-the-art ASU process is highly integrated and nonlinear, which can significantly restrict its ramping rate. In this work, we study the fundamental dynamics of a state-of-the-art double-column ASU, focusing on the dynamic characteristics of the highly integrated and nonlinear heat and mass transfers, and we propose basic control methods for achieving high process ramping rates. We found that the vapor–liquid countercurrent flows in the low-pressure column are critical to the cryogenic rectification of air, which governs the ramp rate of the ASU. This countercurrent flow structure is created through a complex heat integration process in the ASU. Here, this process is simplified as a countercurrent heat transfer to reduce the complexity of studying the ASU dynamics. To preserve this flow structure, the heat integration is maintained so that its heat duty follows the ASU load, using several basic controllers on the critical stream flowrates. A flow-driven dynamic ASU model is built in Aspen Plus Dynamics to capture the basic ramping dynamics. This model revealed a fundamental mismatch in the dynamics in the ASU column that causes a significant loss of O 2 product purity when ramping down the ASU and slightly increases the purity when ramping up. Based on these findings, we propose a basic control method for rapidly ramping down/up the ASU while maintaining O 2 product purity. Simulation results show the ASU basic dynamic process successfully ramps at a rate up to 10 %/min (40–100 % load) while maintaining the O 2 product purity at 95.2–95.6 mol%.

42 ENGINEERING↗

Mass Transport Limitations and Kinetic Consequences of Corn Stover Deacetylation

Alkaline pretreatment of herbaceous feedstocks such as corn stover prior to mechanical refining and enzymatic saccharification improves downstream sugar yields by removing acetyl moieties from hemicellulose. However, the relationship between transport phenomena and deacetylation kinetics is virtually unknown for such feedstocks and this pretreatment process. Here, we report the development of an experimentally validated reaction–diffusion model for the deacetylation of corn stover. A tissue-specific transport model is used to estimate transport-independent kinetic rate constants for the reactive extraction of acetate, hemicellulose and lignin from corn stover under representative alkaline conditions (5–7 g L -1 NaOH, 10 wt% solids loadings) and at low to mild temperatures (4–70°C) selected to attenuate individual component extraction rates under differential kinetic regimes. The underlying transport model is based on microstructural characteristics of corn stover derived from statistically meaningful geometric particle and pore measurements. These physical descriptors are incorporated into distinct particle models of the three major anatomical fractions (cobs, husks and stalks) alongside an unsorted, aggregate corn stover particle, capturing average Feret lengths of 917–1239 μm and length-to-width aspect ratios of 1.8–2.9 for this highly heterogeneous feedstock. Individual reaction–diffusion models and their resulting particle model ensembles are used to validate and predict anatomically-specific and bulk feedstock performance under kinetic-controlled vs. diffusion-controlled regimes. In general, deacetylation kinetics and mass transfer processes are predicted to compete on similar time and length scales, emphasizing the significance of intraparticle transport phenomena. Critically, we predict that typical corn stover particles as small as ~2.3 mm in length are entirely diffusion-limited for acetate extraction, with experimental effectiveness factors calculated to be 0.50 for such processes. Debilitatingly low effectiveness factors of 0.021–0.054 are uncovered for cobs—implying that intraparticle mass transfer resistances may impair observable kinetic measurements of this anatomical fraction by up to 98%. These first-reported quantitative maps of reaction vs. diffusion control link fundamental insights into corn stover anatomy, biopolymer composition, practical size reduction thresholds and their kinetic consequences. These results offer a guidepost for industrial deacetylation reactor design, scale-up and feedstock selection, further establishing deacetylation as a viable biorefinery pretreatment for the conversion of lignocellulosics into value-added fuels and chemicals.

09 BIOMASS FUELS↗

Corrosion Electrochemistry of Chromium in Molten FLiNaK Salt at 600 °C

The manuscript revisits the corrosion behavior of pure Cr in molten FLiNaK salt at 600 °C from the perspective of corrosion electrochemistry. In this work, the potential-dependent, rate-limiting charge-transfer, and salt film-mediated mass-transport controlled regimes of Cr corrosion in FLiNaK at 600 °C are investigated. The kinetic and thermodynamic parameters that limit electrodissolution and the consideration of grain orientation on these regimes are elucidated. At low Cr(III) concentrations, the corrosion process is governed by charge transfer control at low overpotentials and is crystal orientation dependent. However, when Cr(III) concentrations are high or when there is a high overpotential, the formation of a metal fluoride salt film on the Cr surface shifts the kinetic behavior to be governed by mass transport control at all anodic potentials with a surface morphology controlled by salt film deposition location and identity. Evan’s diagrams were developed to consolidate and elucidate these observations. These findings were supported by an examination of the post-corrosion microstructure, X-ray diffraction of solidified salts, and thermo-kinetics analysis in each corrosion regime.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗