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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The effects of in-situ emulsion formation and superficial velocity on foam performance in high-permeability porous media

Foam has been considered as a mobility control agent for Enhanced Oil Recovery (EOR) applications in heterogeneous and fractured reservoirs. Foam enhances sweep efficiency by enabling the injected gas to flow from high-permeability to low-permeability regions. The foam injection velocity is an essential factor affecting foam mobility control and flow behavior. Furthermore, the presence of remaining oil adversely impacts foam generation leading to a failure in governing mobility control. In this study, foam performance in establishing mobility control effect and favorable apparent viscosity was experimentally investigated under a range of total superficial velocities in the presence and absence of crude oil during foam propagation in high permeability sand packs representing a propped fracture network. In the absence of oil, a pronounced effect of total superficial velocity on the mobility control performance was observed at the transition foam quality regime. Co-injection of oil and foam led to noticeable foam destabilization, as expected. However, a further increase in oil fractional flow resulted in larger overall flow resistance. We found that the formation of in-situ surfactant/oil emulsion contributed to the high apparent viscosity exhibited at the steady-state condition. These findings suggest that the steady-state flow resistance established during foam flooding at high oil saturations should be interpreted as the mobility control effect resulting from emulsion formation rather than the development of strong foam.

02 PETROLEUM↗
DOE OSTI2022

Thermo-Hydro-Chemical Simulation of Mid-Ocean Ridge Hydrothermal Systems: Static 2D Models and Effects of Paleo-Seawater Chemistry

Decades of research have resulted in characterization of the ocean floor manifestations of mid-ocean ridge (MOR) hydrothermal systems, yet numerical models accounting for the connections between heat transfer, hydrology and geochemistry have been slow to develop. The Thermo-hydro-chemical code ToughReact can be used to describe the coupled effects of fluid flow, heat transfer, and fluid-rock chemical interactions that occur in MOR systems. We describe the results of 2-dimensional simulations of steady state flow in fractured diabase with mineral-fluid chemical reactions. Basal heating and specified permeability yield maximum temperature of 400°C. Total fluid flux and high fracture flow velocities are in accord with observations. Fluid chemistry, mineralogical changes and 87 Sr/ 86 Sr ratios can be compared to observations to assess and calibrate models. Simulated high temperature fracture fluids have Mg and SO 4 near zero, elevated Ca and 87 Sr/ 86 Sr of about 0.7040. Total alteration is 10%–50% for simple models of spreading. Anhydrite forms mainly near the base of the upwelling zone and results in substantial local fracture porosity reduction. A calibrated model is used to predict how Sr isotopes and other features of altered oceanic crust would be different in the Cretaceous (95 Ma) early Proterozoic (1,800 Ma) and Archean (3,800 Ma), when seawater may have had high Ca and Sr concentrations, lower pH, higher temperature, and lower Na, Mg, and SO 4 . The simulations are offered as a start on what ultimately may require a longer-term community effort to better understand the role of MOR thermo-hydro-chemical systems in Earth evolution.

58 GEOSCIENCES↗
DOE OSTI2021

Influence of turbulence intensity on vortex pattern for a rigid cylinder with turbulence stimulation in flow induced oscillations

The effect of ambient turbulence intensity on the flow induced oscillations of rigid circular cylinders with symmetric and asymmetric local turbulence stimulation is studied. Cylinders oscillate in one degree of freedom transversely to a steady uniform flow. Two-dimensional unsteady Reynolds-Average Navier-Stokes equations with the Spalart-Allmaras turbulence model are used to solve the problem numerically. Three freestream turbulence intensity values (0.2%, 1%, 5%) are used to study the influence of turbulence intensity on vortex pattern. Simulation results are compared with experimental data measured in the Marine Renewable Energy Laboratory of the University of Michigan in the range of 30,000 ≤ Re ≤ 110,000. The amplitude ratio, lift coefficient, vortex modes, and the interactions between vortices and cylinders are observed and discussed. In conclusion, major conclusions are: (a) Vortex patterns strongly depend on the freestream ambient turbulence intensity. (b) Low turbulence intensity can generate multi-vortex patterns at high Re. (c) High turbulence intensity results in fewer separations of a shed vortex into multiple vortices inducing emergence of elongated vortex patterns.

42 ENGINEERING↗
DOE OSTI2022

Using Ensemble Data Assimilation to Estimate Transient Hydrologic Exchange Flow Under Highly Dynamic Flow Conditions

Abstract Quantifying dynamic hydrologic exchange flows (HEFs) within river corridors that experience high‐frequency flow variations caused by dam regulations is important for understanding the biogeochemical processes at the river water and groundwater interfaces. Heat has been widely used as a tracer to infer steady‐state flow velocities through analytical solutions of heat transport defined by the diurnal temperature signals. Under sub‐daily dynamic flow conditions, however, such analytical solutions are not applicable due to the violation of their fundamental assumptions. In this study, we developed a data assimilation‐based approach to estimate the sub‐daily flux under highly dynamic flow conditions using multi‐depth temperature observations at a 5‐min resolution. If the hydraulic gradient is measured, Darcy's law was used to calculate the flux with permeability estimated from temperature responses below the riverbed. Otherwise, flux was estimated directly by assimilating multi‐depth temperature data at 1‐ or 2‐hr time intervals assuming one‐dimensional flow and heat transport governing equation. By comparing estimated fluxes with model‐generated synthetic truth, we demonstrated that both schemes have robust performance in estimating fluxes under highly dynamic flow conditions. This data assimilation‐based flux estimation method was able to capture the vertical sub‐daily fluxes using multi‐depth high‐resolution temperature data alone, even in the presence of multi‐dimensional flow. This approach has been successfully applied to real field temperature data collected at the Hanford site, which experiences highly dynamic HEFs. Our study shows the promise of adopting distributed 1‐D temperature monitoring to capture spatial and temporal exchange dynamics in river corridors at a watershed scale or beyond.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Active- and transfer-learning applied to microscale-macroscale coupling to simulate viscoelastic flows

Active- and transfer-learning are applied to microscale dynamics of polymer flows for the multiscale discovery of effective constitutive approximations required in viscoelastic flow simulation. The result is macroscopic rheology directly connected to a microstructural model. Micro and macroscale simulations are adaptively coupled by means of Gaussian process regression (GPR) to run the expensive microscale computations only as necessary. This multiscale method is demonstrated with flows of a polymer solution as a model system. At the microscale level dissipative particle dynamics (DPD) is employed to model the fluid as a suspension of bead-spring micro-structures subjected to steady shear flow. The results yield the non-Newtonian viscosity and the first normal stress difference at strain rates as training data used in a GPR model. DPD parameters are calibrated with respect to experimental data for a real polymer solution. Compliance with these data requires adjustment of the DPD model's cutoff radius, which then becomes a function of the second invariant of the strain rate tensor. The FENE-P model is chosen for the macroscale description using the spectral element method (SEM) to simulate channel flow and flow past a circular cylinder. The DPD results at the lowest possible shear strain rate yield an estimate of the zero-shear rate viscosity, which allows the initiation of the macroscale flow by SEM as a Newtonian fluid. The resulting strain-rate field is surveyed to determine additional shear strain rate sampling points for the DPD system. This new information allows an initial fitting of parameters of the constitutive equation followed by new SEM simulations at the macroscale. Additionally, guided by active-learning GPR to select new sampling points, this process continues until convergence is achieved. The effectiveness of this new simulation paradigm for viscoelastic flows is tested with different macroscale operating conditions. The effective closure learned in the channel simulation is then transferred directly to the flow past a circular cylinder at low Reynolds number, where the results show that only two additional DPD simulations are required to achieve a satisfactory constitutive model. With an increase of the Reynolds number, the active-learning scheme automatically detects the inaccuracy of the learned constitutive model, and initiates additional DPD simulations for the extra data needed to once again close the microscale-macroscale coupled system. This new paradigm of active- and transfer-learning for multiscale modeling is readily applicable to other microscale-macroscale coupled simulations of complex fluids and other materials. Furthermore, the coupling between microscale and macroscale solvers can be seamlessly implemented with our open source multiscale universal interface (MUI) library.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Simulations of Water Flow in Relation to a Steady Criticality in an Unsaturated Alluvial Repository

Oak Ridge National Laboratory (ORNL) is examining the conditions under which a criticality event could be ruled out for large packages placed in an unsaturated alluvial repository. This work specifically examines the water level in a stylized waste package that is assumed (1) to fail on the top, and (2) to empty as water is driven away—not by boiling—but by fluid flow phenomena driven by thermal gradients. This analysis uses the PFLOTRAN code package. Specifically, this year’s work includes examination of the heat rate at which water is driven away for various percolation rates using the same assumptions listed in the 2022 annual report. The STANDARDS (formerly UNF-ST&DARDS) package has predicted dual-purpose canister (DPC) neutron multiplication factors (k-effectives) ranging above 1.1 (unitless) with failed components. The DPC designs were not created with the intent to use for disposal purposes. Emplacing such packages may be worth consideration if it can be shown that criticality is either extremely unlikely or of very low consequence to the repository’s safety case. This work aims to help establish hydrologic boundary conditions for a highly hypothetical, highly stylized subsurface criticality event. The approach to critical is assumed to be slow, producing steady heating rates under a few kilowatts. For a DPC containing capillary media, the simulated power required for dry-out was proportional to the percolation rate but was unaffected by the size of a large breech on top of the DPC. Results for single cases with no capillary media in the DPC suggest that higher infiltration rates may be required in those cases to cause flooding. Bounding mechanisms and assumptions must be identified and characterized further by performing additional perturbations to various input parameters to demonstrate robustness of the results. This might be accomplished by examining responses to power pulses to determine the system transfer function required to enable a reduced order feedback model.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Flow Channeling in Fracture Networks: Characterizing the Effect of Density on Preferential Flow Path Formation

Flow channelization is a commonly observed phenomenon in fractured subsurface media where the flow of fluids is restricted primarily to highly transmissive fracture networks surrounded by a low-permeability rock matrix. The multiscale structural heterogeneity of these networks results in multiscale flow channelization where preferential flow paths form at length scales ranging from the entire system down to the subfracture size. We present an analysis of how one of the largest scales in fractured media, the network density, influences the degree of flow channeling that occurs using an ensemble of semigeneric three-dimensional discrete fracture network (DFN) simulations. We construct 10 DFNs, whose fracture lengths follow a power law distribution, at four densities for a total of 40 networks. We characterize their structure in terms of the network topology and geometry. Eulerian and Lagrangian observations of the steady-state flow fields obtained within the networks are used to quantify the degree of flow channelization at the network scale. We introduce a measure for the importance-ranking/hierarchy of different flow paths in the network using graph-based analysis of Lagrangian transport by which the degree of flow channeling between networks is compared. These flow observations are then linked to the structural properties of the networks. In general, network-scale flow channeling decreases as the network density increases. However, at low densities, there is more uniform flow within the entire connected network than in high-density networks. We also demonstrate how standard transport observables can be used to infer the degree of flow channelization occurring within a fracture network.

58 GEOSCIENCES↗
DOE OSTI2021

Performance evaluation of a Terry GS-2 steam impulse turbine with air-water mixtures

Terry steam turbines are widely used in various industries because of their robust design. Within the nuclear power generation industry, they are used in the Reactor Core Isolation Cooling System to remove decay heat during reactor isolation events. During the Fukushima Daiichi nuclear power station disaster in Japan in 2011, the Reactor Core Isolation Cooling System and associated Terry turbine operated for over 70 hours in Unit 2; this runtime is well beyond the expected operating duration. Theories suggest the turbine was subjected to a two-phase inlet flow, which could degrade the turbine performance. In this work, an experimental test rig was constructed to test a full-scale Terry model GS-2 steam turbine under two-phase air/water flows. Steady-state efficiency and torque performance maps of the turbine were developed over a range of turbine inlet pressures (1.38–4.83 bar or 20–70 psia), air mass fractions (0.05–1.0) and rotational speeds up to 4000 RPM. Furthermore, turbine performance followed expected trends with torque varying linearly and efficiency varying quadratically with rotational speed. In addition, high-speed images of the two-phase flow entering the turbine were also analyzed to understand how changes in inlet pressure and air mass fraction affect the flow regime and homogenization. The present tests with air–water two-phase mixtures are an important step towards providing an understanding of the full-scale Terry turbine’s behavior and performance curves under two-phase conditions. The results of this work will be combined with air/water and steam/water data gathered using a small-scale Terry ZS-1 steam turbine in order to understand the scaling relationship between large and small size Terry turbines and fluid pairs. The combined data set will enable further development of analytical models over a wide range of conditions and may be used to provide technical justification for expanded use of the Terry turbines in nuclear power plant safety systems and other systems.

42 ENGINEERING↗
DOE OSTI2022

Development of electrostatic precipitator (ESP) technology to remove elemental mercury vapor, HG(0)

The presence of mercury vapor or other forms of mercury presents issues with worker safety, decommissioning facilities, and environmental impacts. As such, it is desired to develop a strategy to either remove or reduce mercury levels in Oak Ridge’s Y-12 Complex facilities. A testing methodology was developed to evaluate electrostatic precipitator technology for removal of mercury vapor. This methodology involved supplying mercury vapor-containing air to the ESP device by flowing air through a column containing alternating layers of sand and liquid mercury droplets. Initial attempts at quantifying the efficacy of the ESP device in removing mercury vapor were plagued with difficulties in controlling the flow of mercury into the ESP device due to poor performance of the generator column and the contamination of these experiments with mercury from an unknown source. These issues were resolved by creating a new generator column with slower air velocity and higher surface area of liquid mercury, along with moving the air intake for the ESP device to outside of the chemical hood in which testing took place. This resulted in a steady, quantified flow of mercury vapor from the generator column and no observation of unintended mercury sources. A final test of the ESP device under these controlled conditions showed that for a certain amount of time (on the order of 20-30 minutes) mercury concentrations were reduced by approximately 33 - 67% of the inlet concentration. However, episodic releases or pulses of mercury observed only at the outlet indicated that the mercury accumulated in the ESP device is periodically expelled. As a result, it was not deemed to be an efficient strategy for the removal of elemental mercury vapor.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Advanced Computational Modeling of High-Level Waste Vitrification at the Hanford Site

The U.S. Department of Energy (DOE) has selected vitrification for stabilizing legacy tank waste at the Hanford site, where radioactive waste from plutonium production was historically stored in underground tanks. This waste will be separated into low-activity waste (LAW) and high-level waste (HLW) fractions and processed at the Waste Treatment and Immobilization Plant (WTP). At WTP, glass melters are used for the vitrification of radioactive tank waste, transforming it into a stable borosilicate glass form for safe long-term storage. The melter vessel is constructed from highly durable and heat-resistant materials, where the vitrification process occurs. The main regions that are modeled are the melt pool, plenum, cold cap, riser/discharge chamber, and surrounding structure with insulation layers. Forced convection induced by air bubblers at the base of the melter ensure uniform temperature distribution and provide heat to the cold cap layer. The cold cap is a region of reacting batch feed that floats on top of the molten glass and is where the batch-to-glass reactions occur. Joule heating provided by electrodes mounted along the vertical walls of the melter and immersed directly in the glass, generates the necessary heat for the net endothermic conversion processes that occur in the cold cap. The high temperatures, radioactivity, and opaque nature of the glass prevent direct observation inside the melters. Therefore, computational models are essential for providing insight into factors that affect melter throughput. Thermocouples in the plenum provide operators with plenum temperature measurements. Operational adjustments include bubbling rate, voltage supplied to the electrodes, feed adjustments, and glass removal rate. Different computational fluid dynamics (CFD) models have been developed, each serving a specific purpose. There are CFD models of different scale melters, as well as models that capture the two-phase flow interfaces of rising bubbles in the molten glass or models with a simplified molten glass region so that the surrounding structure and plenum can be feasibly incorporated. Pilot-scale melter models have been developed to serve as validation of the methods employed in the simulation of the full-scale WTP melters. Models incorporating resolved bubbling are used to develop momentum source terms to implement into a single phase, multi-region, steady-state flow model that is being validated by measured process parameters such as glass production rate, voltage, input power, plenum temperatures, etc. The resolved bubbling model uses the multiphase volume of fluid approach to model the system with a high-resolution interface capturing scheme to maintain sharp interfaces between the molten glass and the air phase. The suite of CFD models is continually being improved to incorporate more realistic physics and achieve faster turnaround time. For example, an incremental controller is implemented to automatically adjust electrode voltage within the simulation to a molten glass set point temperature of 1150°C. Newer models feature improved meshes to ensure conformal meshes between regions and eliminate unnecessary mesh refinement in areas that are not of interest (such as boundary layers in offgas ports). Instead of explicitly modeling the structural, refractory, and insulation layers of the melter, a thermal resistance approach is used with published correlations used for boundary conditions. The development of robust and efficient CFD models will be instrumental in enabling the WTP to successfully fulfill its mission of safely stabilizing legacy nuclear waste.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗
DOE OSTI2021

On the Representation of Hyporheic Exchange in Models for Reactive Transport in Stream and River Corridors

Efforts to include more detailed representations of biogeochemical processes in basin-scale water quality simulation tools face the challenge of how to tractably represent mass exchange between the flowing channels of streams and rivers and biogeochemical hotspots in the hyporheic zones. Multiscale models that use relatively coarse representations of the channel network with subgrid models for mass exchange and reactions in the hyporheic zone have started to emerge to address that challenge. Two such multiscale models are considered here, one based on a stochastic Lagrangian travel time representation of advective pumping and one on multirate diffusive exchange. The two models are formally equivalent to well-established integrodifferential representations for transport of non-reacting tracers in steady stream flow, which have been very successful in reproducing stream tracer tests. Despite that equivalence, the two models are based on very different model structures and produce significantly different results in reactive transport. In a simple denitrification example, denitrification is two to three times greater for the advection-based model because the multirate diffusive model has direct connections between the stream channel and transient storage zones and an assumption of mixing in the transient storage zones that prevent oxygen levels from dropping to the point where denitrification can progress uninhibited. By contrast, the advection-based model produces distinct redox zonation, allowing for denitrification to proceed uninhibited on part of the hyporheic flowpaths. These results demonstrate that conservative tracer tests alone are inadequate for constraining representation of mass transfer in models for reactive transport in streams and rivers.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Reverse segregation and self-organization in inclined chute flows of bidisperse granular mixtures

In the usual segregation scenario for stable inclined chute flows of bidisperse mixtures of fine and coarse spherical particles, coarse particles rise toward the free surface, forming a coarse-rich region atop the flowing pile. Beyond a threshold coarse-to-fine diameter ratio of approximately 4, conversely, the weight of the coarse particles exceeds the segregation driving forces, causing individual coarse particles to sink within the pile and producing a reversed segregation state. However, an understanding of the collective evolution of the pile structure is still lacking when the particle diameter ratio exceeds 4 and the coarse-particle mass fraction is appreciable. To explore this broadly bidisperse limit, we perform discrete element method simulations considering mean particle diameter ratios of up to 8 and coarse-particle mass fractions spanning 0.1 to 0.9. The steady-state flow profiles reveal several intriguing behaviors that depend on the diameter ratio and mass fraction. These include a previously identified transition from usual to reverse segregation and a newfound tendency to self-organize into alternating coarse- and fine-rich particle layers stacked along the shear gradient direction, with layer thickness dictated by the coarse-particle diameter. A fuller understanding of segregation at this scale could pave the way for enhanced mixing or demixing techniques at the commercial scale.

granular flow↗
DOE OSTI2020

Seasonal to Decadal Variability in Focused Groundwater and Contaminant Discharge along a Channelized Stream

Abstract Focused groundwater discharge to streams is problematic at contaminated sites because high fluxes can limit natural attenuation in the hyporheic zone. However, information on location, spatial evolution, and temporal persistence of springs in unlithified sediments over multiyear time scales is limited. We examine discharge at point (~1‐m) to reach (~300‐m) scales along a stream that intercepts trichloroethene and technetium‐99 plumes from a Superfund site. During 2011 to 2012, we seasonally monitored stream and spring flow and contaminant concentrations, along with probing streambed temperatures on a grid in winter and summer, building on prior monitoring during 1999 to 2002. Baseflow measured by both gauging and dye dilution generally increased with distance downstream, and stream and spring discharge varied seasonally, from minima in October to January to maxima in February to June. Thermal anomalies identified by probing occupied approximately 3% to 6% of the reach and typically coincided with visible springs or seeps. Locations of anomalies were similar to those identified in summer 2002, although some orifices disappeared and others emerged. Vertical groundwater fluxes calculated from probing tended to be less than net fluxes calculated from stream discharge, perhaps in part because the assumption of one‐dimensional, steady‐state flow in calculating point fluxes was simplistic. Maximum contaminant concentrations and fluxes decreased between 1999 to 2001 and 2011 to 2012 as a result of partial capture by an upgradient pump‐and‐treat system. Our findings confirm that springs in unlithified sediments can remain stationary within a few meters over decadal time scales, and seasonal variability in discharge can be greater than decadal variability.

Tripathi, Ganesh N.↗
DOE OSTI2024

Optimization strategies for produced water networks with integrated desalination facilities

Optimal management and desalination of produced water is a major challenge for U.S. oil and gas development. Integrating rigorous desalination models into multi-period produced water network optimization problems presents several hurdles, which need to be tackled using advanced optimization strategies. Here, in this work, a novel multi-period produced water network formulation with separate solid and liquid flows is introduced to avoid singularities at zero flows. Rigorous steady state desalination models based on mechanical vapor recompression are embedded at the desalination sites in the network model. An integrated optimization formulation is developed to co-optimize the design of desalination units along with the operation of the network. Furthermore, a more robust approach based on the trust region filter method is developed to efficiently integrate complex desalination models into the multi-period planning problem. Both optimization approaches are demonstrated on a produced water network from the PARETO library (Drouven et al., 2022) using thermal desalination units. Our results show that while the TRF and integrated approaches have comparable solve times, the TRF approach has better performance reliability in terms of solver convergence. Furthermore, the optimal solution obtained by embedding rigorous models into the network is significantly different than when desalination costs are approximated using simple cost models, which motivates further research in this field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Catalytic Site Requirements for N2O Decomposition on Cu-, Co-, and Fe-SSZ-13 Zeolites

N2O decomposition is investigated on Cu, Co and Fe-exchanged SSZ-13 zeolite catalysts at relatively low metal loadings. The catalysts are synthesized by solution ion exchange, and subjected to X-ray diffraction (XRD), temperature-programed-reduction by H2 (H2-TPR), temperature-programed-reaction of N2O (N2O-TPR) coupled with in-situ transmission FTIR, and finally steady-state flow reaction tests. At low N2O pressures (< 0.05 kPa), all catalysts display pseudo first-order kinetics. From Arrhenius analysis, Cu and Fe-SSZ-13 display very different apparent activation energies but similar pre-exponential factors, suggesting their similar reaction mechanisms. N2O decomposition follows a dual-site mechanism, occurring on dimeric M-O-M sites in these catalysts, and O2 is formed by the combination of two O ad-atoms from two vicinal metal sites. Under low N2O pressure (0.05 kPa) and first-order kinetic regime, the reaction is limited by N-O cleavage on bare metal active sites. In comparison to Cu-SSZ-13, the much higher N2O decomposition rate over Fe-SSZ-13 is attributed to the much lower activation barriers for the N-O cleavage step. N2O decomposition occurs on isolated Co2+ ions in Co-SSZ-13. The rate-limiting step is N-O cleavage on an O-occupied Co site in the low-pressure first order kinetic regime. This single-site mechanism leads to much higher pre-exponential factors as compared to the dual-site mechanism. This beneficial factor for reaction rate enhancement, however, is compromised by the much higher activation barriers over this catalyst.

Lin, Fan↗
DOE OSTI2022

Ligand-coordination effects on the selective hydrogenation of acetylene in single-site Pd-ligand supported catalysts

The selective hydrogenation of acetylene to ethylene is a critical step in the synthesis of polyethylenes. Achieving high conversion to ethylene without over-hydrogenation to ethane is a challenge that requires control of the transition metal site, which we achieve through a ligand-coordinated supported catalyst (LCSC) strategy. Using Pd catalysts coordinated to 1,10-phenanthroline-5,6-dione (PDO) ligands on CeO2 supports, we have discovered that the reaction selectivity depends strongly on the ligand:metal ratio with higher selectivity when more ligand is present in the catalyst. Catalyst structure was examined by extended X-ray absorption fine structure spectroscopy, transmission electron microscopy, and CO adsorption, which indicate single-atom character of the Pd. The ligand:metal ratio is determined by Xray photoelectron spectroscopy measurements and correlated with hydrogenation reactions under steady-state flow conditions to examine trends in hydrogenation activity and selectivity. Those trends can be better understood by density functional theory calculations that indicate hydrogen binding on the ligand to guide reaction selectivity toward the desired ethylene hydrogenation product. Here these results demonstrate the importance of considering the dynamic character of LCSCs and inform the design of future single-site heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Reactive Capture and Conversion of Carbon Dioxide to Methanol with ZnZrO 2 and Alkali-Promoted Mg 3 AlO x Mixed Oxide Catalytic Sorbents

Reactive capture and conversion (RCC) explores the use of a single-unit process to capture CO 2 and produce a product, in this case, methanol (MeOH). In this study, different configurations of a catalytic sorbent (CS) composed of ZnZrO 2 catalyst and Mg 3 AlO x sorbent with and without alkali modification are evaluated for CO 2 adsorption, steady-state catalysis with cofed CO 2 and H 2 , and transient RCC performance. A catalyst composed of a physical mixture of Mg 3 AlO x with ZnZrO 2 resulted in a slight increase in CO 2 uptake, with a low impact on the catalytic activity and RCC of the materials compared to ZnZrO 2 alone. In contrast, Na impregnation significantly increased the level of CO 2 uptake from 0.28 mmol/g (ZnZrO 2 alone) to 0.6 and 1.1 mmol/g for the CS with Na on the catalyst or Mg 3 AlO x , respectively. However, Na impregnation reduced the CO 2 conversion rate and MeOH selectivity during steady-state cofeed experiments at 300 °C and 6 bar. In contrast to steady-state catalysis conditions, RCC, which is a cyclic capture and conversion process, creates dynamic CO 2 and H 2 surface coverages, favoring CH 4 in the early stages of the conversion step and then CO and MeOH as the catalyst CO 2 coverage reduces. The highest MeOH productivity during RCC was achieved with CS that balanced the CO 2 uptake with only moderate catalyst rate reductions caused by Na addition. The optimal material, ZnZrO 2 +10%Na/Mg 3 AlO x , achieved a CO 2 uptake of 0.8 mmol/g and a MeOH productivity of 0.5 mmol/g with 100% selectivity at 260 °C and 6 bar during RCC. This marks the highest RCC MeOH productivity reported to date, although the process needs further optimization and even with optimization, may remain impractical. The results further demonstrate that optimization of catalytic sorbents under steady-state flow conditions does not easily correlate to transient capture and conversion cycles for methanol synthesis from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗