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Results for “Partial Oxidation Chemistry”

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
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

CFD modeling of non-catalytic, partial-oxidation engine reformer for flare mitigation

Flaring associated natural gas is commonly employed in the oil and gas industry to reduce methane (CH 4 ) emissions but generates carbon dioxide (CO 2 ) and harmful pollutants, significantly contributing to air pollution and posing risks to public health. To mitigate this impact, M2X Energy Inc. has developed a small-scale, modular gas-to-methanol system. This system features an engine reformer that performs fuel-rich partial oxidation of wellhead gas to produce syngas—a mixture of carbon monoxide (CO) and hydrogen (H 2 )—followed by a downstream reactor for methanol synthesis. This study focused on computational fluid dynamics (CFD) modeling of the engine reformer to simulate partial oxidation chemistry, predict the rich-burn operating limit, and assess syngas quality, ultimately aiding in design and operational optimization. The CFD model, developed within a Reynolds-Averaged Navier-Stokes (RANS) turbulence framework, incorporated sub-models for turbulent combustion, a chemical mechanism with polycyclic aromatic hydrocarbon (PAH) pathways, and soot emissions to accurately capture the fuel-rich, turbulent jet ignition and combustion processes. Model validation against experimental data showed good agreement across pre- and main-chamber pressures, apparent heat release rates, and exhaust gas concentrations of key species (H 2 , CO, CO 2 , CH 4 ) for varying intake equivalence ratios. Here, the model identified a rich-burn operating limit near a fuel-air equivalence ratio of 2.35, consistent with experimental observations. Furthermore, syngas quality analysis revealed that extending the rich-burn limit through engine reformer optimization could enhance syngas production, contributing to higher methanol synthesis efficiency.

Computational Fluid Dynamics↗
DOE OSTI2024

Surface chlorination of IrO2(110) by HCl

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.

Chemistry↗
DOE OSTI2020

Near-Surface Imaging of the Multicomponent Gas Phase above a Silver Catalyst during Partial Oxidation of Methanol

Fundamental chemistry in heterogeneous catalysis is increasingly explored using operando techniques in order to address the pressure gap between ultrahigh vacuum studies and practical operating pressures. Because most operando experiments focus on the surface and surface-bound species, there is a knowledge gap of the near-surface gas phase and the fundamental information the properties of this region convey about catalytic mechanisms. In this work, we demonstrate in situ visualization and measurement of gas-phase species and temperature distributions in operando catalysis experiments using complementary near-surface optical and mass spectrometry techniques. The partial oxidation of methanol over a silver catalyst demonstrates the value of these diagnostic techniques at 600 Torr (800 mbar) pressure and temperatures from 150 to 410 °C. Planar laser-induced fluorescence provides two-dimensional images of the formaldehyde product distribution that show the development of the boundary layer above the catalyst under different flow conditions. Raman scattering imaging provides measurements of a wide range of major species, such as methanol, oxygen, nitrogen, formaldehyde, and water vapor. Near-surface molecular beam mass spectrometry enables simultaneous detection of all species using a gas sampling probe. Detection of gas-phase free radicals, such as CH 3 and CH 3 O, and of minor products, such as acetaldehyde, dimethyl ether, and methyl formate, provides insights into catalytic mechanisms of the partial oxidation of methanol. The combination of these techniques provides a detailed picture of the coupling between the gas phase and surface in heterogeneous catalysis and enables parametric studies under different operating conditions, which will enhance our ability to constrain microkinetic models of heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Investigation of the Mechanisms Underpinning Plasma-Catalyst Interaction for the Conversion of Methane to Oxygenates

Plasma catalysis is a promising approach to further enhance the conversion of methane into value-added products such as methanol. In this work, the mechanisms enabling the conversion of methane to CO, CO 2 and methanol enabled by plasma-enhanced catalysis were investigated. A catalyst reactor was incorporated downstream of the plasma jet to enable the separation between plasma generation and the catalyst bed. An enhancement in CH 3 OH and CO 2 production was observed for the shortest distance between the plasma and catalyst compared to the plasma-only case. Plasma-enabled gas heating was shown not to be responsible for the observed synergy while a gas temperature increase as low as 30-40 K significantly impacted desorption rates of CH 3 OH/C 2 H 5 OH on alumina particles. Correlations between molecular beam mass spectrometry (MBMS) measurements at the inlet and outlet of the catalytic reactor suggest that the observed synergistic effect was caused by radical species most likely the CH 3 O 2 radical. As a result, this study shows that surface reactions induced by radicals such as alkylperoxy radicals might play an important role in surface reactions in plasma-catalysis.

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

Activation of propane on Ag–PdO(101) model surfaces

Oxidation of alkanes remains a central challenge in catalysis due to the high activation barriers of C–H bonds and the thermodynamic favorability of complete oxidation. Palladium oxide (PdO), particularly its (101) facet, is known for its high reactivity in alkane oxidation, which is attributed to its coordinatively unsaturated palladium (Pd) and O atoms. In this study, we investigate the effect of silver (Ag) incorporation on the oxidation behavior of propane over PdO(101) using temperature-programmed reaction spectroscopy (TPRS) under controlled conditions. While pristine PdO(101) exhibits complete oxidation of propane with CO₂ and H₂O desorption at high temperatures (approximately 475 K), Ag incorporation induces a new CO₂ desorption peak at significantly lower temperatures (approximately 330 K). This shift is attributed to the formation of new active sites at the Ag–PdO(101) interface. Quantitative analysis reveals that low-temperature activity correlates with Ag coverage, while overall CO₂ production decreases, suggesting a redistribution of reactivity rather than an increase in active surface area. Activation energy estimations using the Redhead method confirm that C–H bond activation becomes more facile at the interface, with a 46 kJ/mol reduction compared to pristine PdO(101). These findings demonstrate that incorporating a less reactive metal such as Ag into PdO surfaces not only modifies the reaction energetics but also enables the design of bimetallic catalysts with improved selectivity for partial oxidation reactions.

Chemistry↗
DOE OSTI2022

Ru-promoted perovskites as effective redox catalysts for CO2 splitting and methane partial oxidation in a cyclic redox scheme

The current study reports AxA’1-xByB’1-yO3- perovskite redox catalysts (RCs) for CO2-splitting and methane partial oxidation (POx) in a cyclic redox scheme. Strontium (Sr) and iron (Fe) were chosen as A and B site elements with A’ being lanthanum (La), samarium (Sm) or yttrium (Y), and B’ being manganese (Mn), or titanium (Ti) to tailor their equilibrium oxygen partial pressures (P_(O_2 ) s) for CO2-splitting and methane partial oxidation. DFT calculations were performed for predictive optimization of the oxide materials whereas experimental investigation confirmed the DFT predicted redox performance. The redox kinetics of the RCs improved significantly by 1 wt.% ruthenium (Ru) impregnation without affecting their redox thermodynamics. Ru impregnated LaFe0.375Mn0.625O3 (A=0, A’=La, B=Mn, and B’=0) was the most promising RC in terms of its superior redox performance (CH4/CO2 conversion >90% and CO selectivity~ 95%) at 800oC. Long-term redox testing over Ru impregnated LaFe0.375Mn0.625O3 indicated stable performance during the first 30 cycles following with a ~25% decrease in the activity during the last 70 cycles. Air treatment was effective to reactivate the redox catalyst. Detailed characterizations revealed the underlying mechanism for redox catalyst deactivation and reactivation. Furthermore, this study not only validated a DFT guided mixed oxide design strategy for CO2 utilization but also provides potentially effective approaches to enhance redox kinetics as well as long-term redox catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Evolution and persistence of SiO emission in nanosecond laser ablation plumes

Analyzing laser-produced plasmas in a controlled oxygen-containing environment provides insight into the formation and evolution of molecular species through gas-phase oxidation. This study explores the role of ambient pressure and oxygen availability in forming SiO molecular species in laser ablation plumes. The self-emission emanating during the reactive ablation of Si targets was characterized by optical emission spectroscopy and optical time-of-flight techniques. Our results showed that the SiO species formation was greatly influenced by both the ambient pressure and oxygen availability. The intensity and the persistence of SiO emission bands are lower at higher oxygen concentrations, indicating they are depopulated by the formation of more complex silicon oxides. The oxygen partial pressure effects on plume chemistry showed that SiO formation is favored even with a minimal oxygen concentration in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Continuous partial oxidation of methane to methanol over Cu-SSZ-39 catalysts

Here, the direct conversion of methane to methanol using molecular oxygen as the oxidant is a grand challenge in the chemical sciences. Here we describe our efforts in using copper-exchanged SSZ-39 for this chemistry and show it is a promising material for this reaction. Testing in a continuous flow reactor at 225 °C, Cu-SSZ-39 showed superior activity for methane partial oxidation compared to Cu-SSZ-13 (site time yields of 26.9 ± 0.8 mol CH3OH ·mol Cu -1 ·h -1 *10 -3 versus 13.2 mol CH3OH ·mol Cu -1 ·h -1 *10 -3 respectively). A clear maximum in methanol productivity, both in terms of a mass catalyst basis and copper atom basis is observed for Cu-SSZ-39 at a Cu/Al ~ 0.2. Running this reaction in the absence of oxygen over samples with a Cu/Al > 0.1 the reactivity is markedly lower than that in the presence of oxygen unlike what is observed in SSZ-13.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Mechanistic Studies of Continuous Partial Methane Oxidation on Cu−Zeolites Using Kinetic and Spectroscopic Methods

Abstract Over the past few decades, a significant amount of research effort has focused on investigating the active site requirements and reaction mechanisms for partial methane oxidation (PMO) to methanol over copper–exchanged zeolites during stoichiometric and stepwise chemical looping routes. More recently, research efforts have expanded to include investigating the PMO reaction in a continuous catalytic regime, primarily focusing on determining the influence of catalyst composition on Cu speciation and structure and, in turn, on PMO rate and selectivity. The structures of candidate Cu active sites are commonly studied using a combination of ex situ and in situ spectroscopic approaches. In this perspective, we critically examine the prior literature on catalytic PMO over Cu–zeolites to identify key knowledge gaps that remain in our understanding as motivation for future research efforts. We identify opportunities for future research to address these gaps by adapting analogous interrogation techniques that have been successfully used to elucidate the active site requirements and mechanistic details of another catalytic redox reaction cycle on Cu–zeolites, the selective catalytic reduction (SCR) of nitrogen oxides (NO x ).

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

Partial oxidation of isobutylene using Ni TiO x

In this work, we report an aerobic partical oxidation of isobutylene into isoprene, acetone, and p-xylene using a mesoporous Ni TiO x catalytic material. In this work, two catalysts were found to synthesize two of these three valuable products with high selectivity, with p-xylene being synthesized with a selectivity of 46.0% and isoprene being synthesized with a selectivity of 64.7%, with overall conversions of isobutylene being 34.0% and 11.9% respectively. These reactions were done at relatively low temperatures. (300°C or below) and are conducted at flow rates of 10 sccm oxygen and isobutylene. The nickel titania catalysts were studied extensively using various characterization methodologies such as TEM, Raman, XRD, and XRF.

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

Heterogeneous and Framework-Bound Copper Species Contribute to Catalytic Partial Methane Oxidation in Cu–Chabazite Zeolites

The relationship between continuous partial methane oxidation (PMO) rates and Cu site speciation in Cu-CHA zeolite catalysts is explored through differential rate measurements across a series of samples of varying compositions combined with density functional theory, first-principles thermodynamics, and statistical models that characterize Cu speciation. Under continuous PMO conditions (573 K, 0.07 kPa O 2 , 3 kPa H 2 O), Cu ions are shown to anchor to the CHA framework in both monomeric (Z 2 Cu and Z 2 CuH 2 O) and dimeric (O- and OH-bridged Cu) forms that are sensitive to the identity of the local framework anchoring site. Consequently, across the studied compositional range, Cu-CHA catalysts are predicted to contain a mixture of monomeric and dimeric Cu sites. Cu-normalized CH 3 OH formation rates extrapolated to zero conversion reflect contributions from multiple site types. Predicted CH 3 OH formation rates indicate that the Cu site reactivity toward CH 4 is influenced by zeolite composition and is likely limited by the reduction half-cycle.

03 NATURAL GAS↗
NASA NTRS1977

Prediction of hydrodynamics and chemistry of confined turbulent methane-air flames with attention to formation of oxides of nitrogen

A formulation of the governing partial differential equations for fluid flow and reacting chemical species in a tubular combustor is presented. A numerical procedure for the solution of the governing differential equations is described, and models for chemical equilibrium and chemical kinetics calculations are presented. The chemical equilibrium model is used to characterize the hydrocarbon reactions. The chemical kinetics model is used to predict the concentrations of the oxides of nitrogen. The combustor consists of a cylindrical duct of varying cross sections with concentric streams of gaseous fuel and air entering the duct at one end. Four sample cases with specified inlet and boundary conditions are considered, and the results are discussed

Elghobashi, S.↗
DOE OSTI2025

Capture of volatile RuO 4 from oxidized simulated used nuclear fuel solutions

Ruthenium is a challenging fission product in used nuclear fuel (UNF) reprocessing due to its complex redox chemistry, variable speciation in nitric acid, partial extractability, and volatility. This work presents a strategy for Ru removal based on the volatilization of RuO 4 using the strong oxidant sodium bismuthate, followed by RuO 2 deposition onto various substrates. Among the materials tested, polymer-based substrates such as polyolefin wax film (Parafilm®), exhibited superior performance, achieving up to near-quantitative Ru removal from solution. After dissolution of the substrate, 99.6% of the Ru was recovered as RuO 2 . The deposition mechanism onto the polyolefin wax film involves both physisorption and chemical reaction through oxidative cleavage of olefinic bonds within the polymer. In contrast, on inorganic substrates such as Al foil, RuO 4 undergoes incomplete surface adsorption and reduction, as confirmed by FTIR and XPS analyses. This approach remains effective under conditions of simulated oxidation of UNF solutions, selectively removing Ru while leaving other fission products in solution. As a result, capture of RuO 4 offers a practical and efficient strategy for ruthenium decontamination and recovery, offering a route for integration into existing UNF reprocessing flowsheets to enhance overall process safety and performance.

Ruthenium↗
DOE OSTI2026

Transient Catalytic Reaction Analysis Through Signal Defragmentation

The Temporal Analysis of Products (TAP) pulse response technique provides valuable insights into catalytic function and reaction kinetics. However, complex fragmentation patterns in the TAP mass spectrometry signals can complicate precise quantification, particularly when analyzing transient gas flux data typical of TAP experiments. This work demonstrates a standard defragmentation method that deconvolves transient TAP signals while maintaining the temporal resolution of the experiment. First, the integrals of calibration gas fluxes are used to determine the fingerprint fragmentation pattern and construct a fragmentation matrix. This matrix is then used to defragment experimental flux data at each recorded time point via a non-negative least squares regression. The effectiveness of this method is demonstrated using virtual data and control experiments with a TAP reactor system. The defragmentation is then applied to the more complex propane dehydrogenation reaction on a chromia/alumina catalyst, which can contain up to ten significant gas species in the reactor outlet. Initial propane pulsing reveals an induction period during which propane is fully oxidized to CO2, followed by partial reduction to CO. Afterwards, there is a transition in chemistries towards coking and propylene production. Our example illustrates a practical method for the accurate determination of the time-dependent reactant/product concentrations and rates for a thorough analysis of the propane dehydrogenation kinetics. This approach can be broadly applied to any transient mass spectrometry experiment for a better understanding of catalyst-reaction dynamics.

36 - MATERIALS SCIENCE↗
NASA NTRS2010

Low-Degree Partial Melting Experiments of CR and H Chondrite Compositions: Implications for Asteroidal Magmatism Recorded in GRA 06128 and GRA 06129 T

Studies of differentiated meteorites have revealed a diversity of differentiation processes on their parental asteroids; these differentiation mechanisms range from whole-scale melting to partial melting without the core formation [e.g., 1]. Recently discovered paired achondrites GRA 06128 and GRA 06129 (hereafter referred to as GRA) represent unique asteroidal magmatic processes. These meteorites are characterized by high abundances of sodic plagioclase and alkali-rich whole-rock compositions, implying that they could originate from a low-degree partial melt from a volatile-rich oxidized asteroid [e.g., 2, 3, 4]. These conditions are consistent with the high abundances of highly siderophile elements, suggesting that their parent asteroid did not segregate a metallic core [2]. In this study, we test the hypothesis that low-degree partial melts of chondritic precursors under oxidizing conditions can explain the whole-rock and mineral chemistry of GRA based on melting experiments of synthesized CR- and H-chondrite compositions.

Usui, T.↗