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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Optimizing the lean hydrocarbon NO x trap: Sequential and dual-layer configurations

Vehicular emission control catalysts are ineffective in eliminating CO, hydrocarbons, and NO x during engine cold-start when exhaust temperatures are below 200 °C. In this study the performance of coupled low temperature NO x , n-C 12 H 26 (C 12 ), and C 3 H 6 trapping, release and conversion for a series of model Lean Hydrocarbon NO x Trap (LHCNT) catalysts are examined. Pd and Pt supported on small-pore (SSZ-13) and large-pore (BEA) zeolites are selected based on the performance during transient NO and C 12 uptake, release and conversion experiments. These catalysts are combined into sequential (Pt + Pd/BEA → Pd/SSZ-13; Pd/SSZ-13 → Pt + Pd/BEA) and dual-layer (Pt + Pd/BEA top, Pd/SSZ-13 bottom) configurations in an attempt to improve the trapping and conversion performance. While all three configurations trap between 75 and 100 μmolNO x /g-cat, the Pd/SSZ-13 → Pt + Pd/BEA sequential configuration is most effective in simultaneously trapping C 12 and NO in the presence of H 2 O, resulting in excellent NO and C 12 storage below 100 °C with release and/or conversion at or above 200 °C. For each configuration, C 12 oxidation lights-off below 300 °C and NO oxidation achieves ~35 % conversion in the absence of C 12 . Neither the presence of C 12 nor the order of the sequential configuration has a significant impact on NO uptake. C 12 significantly delays NO and NO 2 desorption to temperatures exceeding 300 °C. The more compact dual-layer catalyst is most effective in forming NO 2 as the release temperature lines up with the maximum NO conversion temperature but traps less C 12 than the sequential configurations. The addition of C 3 H 6 in the feed on the dual-layer catalyst leads to further delay in the NO x desorption as well as increased NO and C 12 conversion at high temperatures. Here, the overall findings provide guidance in the optimizing LHCNT configuration for realistic feeds.

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

Molecular Mass Growth Processes to Polycyclic Aromatic Hydrocarbons through Radical–Radical Reactions Exploiting Photoionization Reflectron Time-of-Flight Mass Spectrometry

Polycyclic aromatic hydrocarbons (PAHs) represent critical building blocks in molecular mass growth processes to carbonaceous nanoparticles, referred to as interstellar and circumstellar grains along with soot particles in astrophysical environments and combustion systems, respectively. Recent advancements on elucidating elementary steps to PAHs have utilized reactions of aromatic radicals, resonantly stabilized free radicals, and aliphatic radicals with closed shell hydrocarbons. However, the role of radical–radical reactions (RRRs) leading to PAHs has remained largely unexplored on the molecular level due to preceding experimental challenges in producing sufficiently high number densities of radical reactants for isomer-selective detection of products from bimolecular and termolecular reactions. This Account offers the latest developments in our knowledge on the mechanisms and pathways to PAHs via RRRs probed in a chemical microreactor at temperatures as high as 1600 K. Product preservation in a molecular beam coupled with synchrotron vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and photoelectron photoion coincidence spectroscopy enabled isomer-selective detection of PAHs of up to three rings by their photoionization efficiency curves, which were fit with a linear combination of reference curves for identification. Experiments were combined with computational fluid dynamics modeling of the physicochemical processes in the microreactor, as well as high-level electronic structure calculations to reveal the reaction pathways of each system. Six distinct reaction mechanisms were discovered in this work: propargyl addition─benzannulation (PABA), methyl addition─ring expansion (MARE), cyclopentadienyl addition─naphthylization (CPAN), fulvenallenyl addition─cyclization─aromatization (FACA), benzyl addition─aromatization (BAA), and phenyl addition─pentacyclization (PAP). By systematically varying the number of carbon atoms in the radical reactants, molecular mass growth processes involving reactions between radicals with odd numbers of carbon atoms access aromatics carrying one, two, or three six-membered rings, whereas reactions between even- and odd-carbon-numbered radicals produce aromatics combining five- and six-membered rings. Our investigations reveal unconventional cycloadditions on excited state triplet surfaces, additions of radicals to low spin density carbon-centered radicals, spiroaromatic and fulvene-type intermediates, and highly strained bicyclic reaction intermediates, challenging current perceptions of PAH molecular mass growth processes. All of the listed mechanisms, except for FACA, feature endoergic reactions or barriers which lie above the separated reactants and therefore might be central to circumstellar environments of carbon-rich stars and planetary nebulae as their descendants, but they play no role in the gas phase of cold molecular clouds where temperatures as low as 10 K dominate. Altogether, this work provides detailed reaction mechanisms of PAH growth processes, advancing our knowledge of the chemistry of carbonaceous matter in the universe.

Addition reactions↗
DOE OSTI2026

Oxidation, Oligomerization, Isomerization of Hydrocarbons Using Metal–Organic Frameworks

The selective conversion of hydrocarbons into higher-value fuels and feedstocks is essential to the global energy and chemistry landscape. While porous inorganic materials have enabled significant progress in these transformations, achieving high activity, selectivity, and stability under industrially relevant conditions remains challenging. Metal–organic frameworks (MOFs) are a promising platform to precisely control active-site environments and interrogate structure–function relationships due to their crystallinity, tunability, and porosity. This review highlights relevant hydrocarbon transformations and outlines the general mechanisms for oxidation, oligomerization, and isomerization. Metal node acidity, confinement effects, and active site dispersion are analyzed for their impact on reactivity and selectivity across the three reactions. Lastly, we discuss current limitations in catalyst stability and offer a perspective on integrating reticular chemistry with high-throughput experimentation and machine learning to accelerate the discovery and design of robust, next-generation MOF catalysts.

Catalysts↗
DOE OSTI2025

Customizable Aperture Geometry in Metal–Organic Frameworks for Kinetic Hydrocarbon Separation

Precise control of aperture dimensions is crucial in adsorptive separations of hydrocarbons, as it directly affects key parameters such as selectivity, capacity, diffusion, and recyclability. The development of metal–organic frameworks (MOFs) has enabled the fine-tuning of local pore environments to address important hydrocarbon separations. However, customizing the aperture geometry to tune the kinetic separation performance remains challenging. Here, we deploy a mixed-linker synthesis strategy, combining long and short linkers on fcu net Zr-MOFs with equilateral triangular apertures to construct isoreticular multivariate MOFs, NU-415 and NU-416, with tailored isosceles triangular apertures suitable for the separation of hexane isomers. Sorption, liquid batch separation, and X-ray diffraction measurements demonstrate significantly improved selectivity, capacity, stability, and recyclability of NU-415 and NU-416 compared with Zr-muconate and MOF-801. Notably, both NU-415 and NU-416 achieve uptake capacities of 2.2 mmol g –1 in 1 min with an n-hexane to 2,2-dimethylbutane selectivity over 200 in an equimolar ternary mixture at ambient conditions, comparable to leading reported materials. Mechanistic studies confirm that separation performance is predominantly governed by significant kinetic differences rather than by thermodynamics. Furthermore, the successful customization of aperture geometry not only enables superior linear to monobranched hexane selectivity in NU-415 but also demonstrates the mixed-linker synthesis strategy as a promising solution for precise and predictable pore architecture control in MOFs.

Adsorption↗
DOE OSTI2022

Sulfur cycling at natural hydrocarbon and sulfur seeps in Santa Paula Creek, CA

Biogeochemical cycling of sulfur is relatively understudied in terrestrial environments compared to marine environments. However, the comparative ease of access, observation, and sampling of terrestrial settings can expand our understanding of organisms and processes important in the modern sulfur cycle. Furthermore, these sites may allow for the discovery of useful process analogs for ancient sulfur-metabolizing microbial communities at times in Earth's past when atmospheric O 2 concentrations were lower and sulfide was more prevalent in Earth surface environments. Here, we identified a new site at Santa Paula Creek (SPC) in Ventura County, CA—a remarkable freshwater, gravel-bedded mountain stream charged with a range of oxidized and reduced sulfur species and heavy hydrocarbons from the emergence of subsurface fluids within the underlying sulfur- and organic-rich Miocene-age Monterey Formation. SPC hosts a suite of morphologically distinct microbial biofacies that form in association with the naturally occurring hydrocarbon seeps and sulfur springs. We characterized the geology, stream geochemistry, and microbial facies and diversity of the Santa Paula Creek ecosystem. Using geochemical analyses and 16S rRNA gene sequencing, we found that SPC supports a dynamic sulfur cycle that is largely driven by sulfide-oxidizing microbial taxa, with contributions from smaller populations of sulfate-reducing and sulfur-disproportionating taxa. This preliminary characterization of SPC revealed an intriguing site in which to study geological and geochemical controls on microbial community composition and to expand our understanding of sulfur cycling in terrestrial environments.

58 GEOSCIENCES↗
DOE OSTI2024

Theoretical studies of chemical reactions related to the formation and growth of polycyclic aromatic hydrocarbons (PAH) and molecular properties of their key intermediates (Final Progress Report)

The formation mechanisms of polycyclic aromatic hydrocarbons, (PAHs) – organic molecules carrying fused benzene rings – are of great interest to scientists and engineers due to their importance in combustion chemistry and astrochemistry. On Earth, PAHs are largely produced in incomplete combustion of fossil fuel and are considered as critical precursors to unwanted soot particles leading to combustion inefficiency and causing air pollution along with detrimental health effects. Simple PAH molecules initially formed in the gas phase, are further involved in a build-up process in combustion flames leading to larger PAH, bowl-shaped nanostructures, fullerenes, and solid-phase species including carbonaceous dust, graphene particles, and soot. In deep space, PAH and their derivatives are potential key intermediates and nucleation sites leading eventually to carbonaceous nanoparticles (“interstellar grains”). Therefore, the understanding of the key processes in the synthesis of PAHs along with their precursors and their degradation mechanisms in combustion systems and in interstellar, circumstellar, and planetary atmospheric environments will provide critical insights into how complex aromatic structures, carbonaceous nanoparticles, and fullerenes are formed and destroyed. Achieving this understanding is an important step in the development of the efficient combustion processes and of the ecofriendly devices with reduced environmental pollution as well as technological strategies for the production of hydrogen and solid carbon through thermal or plasma-assisted pyrolysis of natural gas and biomass. Also, the understanding of the key processes of PAH and soot growth will help in our comprehension of chemical evolution in the universe. Detailed information on the mechanisms and reliable rate constants of the key elementary chemical reactions involved in PAH formation and destruction processes and in inception of soot particles is often missing, with the main deficiencies being the absence of temperature- and pressure-dependent rate constants for the broad range of conditions occurring in various terrestrial and interstellar processes and the lack of data on the reaction products and their branching ratios. Complementary to experimental studies, these gaps in knowledge can be filled by using quantum chemical calculations of reaction potential energy surfaces providing us with accurate energies of reaction products, intermediates, and transition states, revealing the reaction mechanism, and giving the molecular properties required to compute rate constants for relevant reaction steps and product branching ratios using the RRKM-Master Equation (ME) method. Molecular dynamics (MD) simulations can be used in cases when a reaction rate cannot be properly described by statistical theories. During the terminal renewal project period we employed these ab initio/RRKM-ME and MD approaches to complete our studies on several key reactions relevant to the formation/growth of PAH and inception of soot particles including (1) the reaction mechanism and kinetics of the resonance stabilized fulvenallenyl radical with propargyl and C 3 H 4 isomers; (2) the reaction mechanism and kinetics for the C + indene and C 2 + styrene reactions producing naphthyl or azulenyl radicals in low-temperature environments; (3) the MD study of non-equilibrium dimerization of acepyrene and coronene and its radical. The information derived from our theoretical calculations contributed to a better fundamental understanding of the reaction mechanisms and provide missing critical kinetic data to improve combustion models of hydrocarbon fuels and astrochemical models of the growth of carbonaceous molecules and particles in cold molecular clouds, circumstellar envelopes, and planetary atmospheres.

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

Catalyst Development to Overcome Barriers for Commercialization of Synthetic High-Octane Hydrocarbons: Cooperative Research and Development (Final Report)

In recent years, researchers at the National Renewable Energy Laboratory (NREL) and the University of California Berkeley (UC Berkeley) have independently developed catalysts that convert methanol and dimethyl ether into alkylate-like hydrocarbons with a high-octane value, and both have developed intellectual property around these chemical transformations. Both UC Berkeley and NREL wish to see their technologies commercialized to address a number of domestic and international energy challenges. The technologies developed by NREL and UC Berkeley are complimentary but neither have moved beyond the laboratory scale due to remaining challenges with the catalyst activity and selectivity, and/or with the reaction engineering associated with maximizing the yield of the high-value product. NREL and UC Berkeley wish to collaboratively through a shared resources CRADA to solve issues related to the scale-up and process integration of their high-octane hydrocarbon technologies, thus enabling future licensing of the technology to an industry partner.

10 SYNTHETIC FUELS↗
NASA NTRS1965

Investigation of light hydrocarbon fuels with flox mixtures as liquid rocket propellants final report, 30 jun. 1964 - 30 jun. 1965

An analysis was completed for determination of the most promising hydrocarbon fuels for use with flox in upper stage rocket engines. Experimental rocket firings in uncooled, transpiration cooled, and regeneratively cooled thrust chambers were conducted using flox with methane, propane, butene-1, and a eutectic blend of pentane and isopentane. Experimental heated tube heat transfer and hypergolicity tests were conducted, and laboratory determinations of physical properties of various blends of hydrocarbon compounds were made.

HYDROCARBON FUEL↗
NASA NTRS1996

Spatial variation of the 3.29 and 3.40 micron emission bands within reflection nebulae and the photochemical evolution of methylated polycyclic aromatic hydrocarbons

Spectra of 3 micrometers emission features have been obtained at several positions within the reflection nebulae NGC 1333 SVS3 and NGC 2023. Strong variations of the relative intensities of the 3.29 micrometers feature and its most prominent satellite band at 3.40 micrometers are found. It is shown that (i) the 3.40 micrometers band is too intense with respect to the 3.29 micrometers band at certain positions to arise from hot band emission alone, (ii) the 3.40 micrometers band can be reasonably well matched by new laboratory spectra of gas-phase polycyclic aromatic hydrocarbons (PAHs) with alkyl (-CH3) side groups, and (iii) the variations in the 3.40 micrometers to 3.29 micrometers band intensity ratios are consistent with the photochemical erosion of alkylated PAHs. We conclude that the 3.40 micrometers emission feature is attributable to -CH3 side groups on PAH molecules. We predict a value of 0.5 for the peak intensity ratio of the 3.40 and 3.29 micrometers emission bands from free PAHs in the diffuse interstellar medium, which would correspond to a proportion of one methyl group for four peripheral hydrogens. We also compare the 3 micrometers spectrum of the proto-planetary nebula IRAS 05341+0852 with the spectrum of the planetary nebula IRAS 21282+5050. We suggest that a photochemical evolution of the initial aliphatic and aromatic hydrocarbon mixture formed in the outflow is responsible for the changes observed in the 3 micrometers emission spectra of these objects.

NASA Center ARC↗
NASA NTRS1999

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

NASA Center ARC↗
DOE OSTI2026

Adsorption-Engineered Hydrocarbon Ionomers for Durable Proton-Exchange Membrane Fuel Cells

Reducing reliance on perfluoroalkyl substances (PFAS) in proton-exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long-term durability, a persistent challenge in catalyst-layer design. Here, we identify oxidation-driven ionomer-catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer-bonded cathodes and introduce an adsorption-engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon-supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm−2 at 0.65 V under fully humidified H2/air conditions (80°C and 150 kPaabs), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)-bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion-bonded cathodes (14%). These findings establish adsorption-engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high-performance PFAS-free PEM fuel cell electrodes.

08 HYDROGEN↗
DOE OSTI2025

Probing Effects of Electron Addition to Polycyclic Conjugated Hydrocarbons Containing Four‐Membered Rings

The rectangular cyclobutadiene (CBD, C 4 H 4 ) is a unique moiety for building nonbenzenoid polycyclic conjugated hydrocarbons with interesting electron‐accepting properties. Herein, the investigation on chemical reduction of several CBD‐containing polycyclic hydrocarbons with increasing conjugation length is reported: biphenylene (C 12 H 8 ), dimethyl[2]naphthalene (C 22 H 16 ), and tetramethyl‐dibenzo‐[3]phenylene (C 30 H 22 ). The two‐step sequential reduction is first demonstrated by in situ spectroscopic investigation and then confirmed by the isolation of single crystals of the reduced products. The X‐ray crystallographic analysis reveals the formation of several mono‐ and doubly reduced products in solvent‐separated and complexed forms. The crystal structures for both neutral parents and corresponding reduced products unravel the changes in bond alternation in each ring of the fused systems. Density functional theory (DFT) and nucleus‐independent chemical shift (NICS) scan calculations reveal that the two‐electron addition reduces the aromatic character in the benzenoid rings but has minor influence on the antiaromatic CBD rings.

Zhu, Yikun [Department of Chemistry University at ↗
DOE OSTI2021

Switching CO 2 Electroreduction Selectivity Between C 1 and C 2 Hydrocarbons on Cu Gas-Diffusion Electrodes

We report that regulating the selectivity toward a target hydrocarbon product is still the focus of CO 2 electroreduction. Here, we discover that the original surface Cu species in Cu gas-diffusion electrodes plays a more important role than the surface roughness, local pH, and facet in governing the selectivity toward C 1 or C 2 hydrocarbons. The selectivity toward C 2 H 4 progressively increases, while CH 4 decreases steadily upon lowering the Cu oxidation species fraction. At a relatively low electrodeposition voltage of 1.5 V, the Cu gas-diffusion electrode with the highest Cu δ+ /Cu 0 ratio favors the pathways of hydrogenation to form CH 4 with maximum Faradaic efficiency of 65.4% and partial current density of 228 mA cm -2 at -0.83 V vs RHE. At 2.0 V, the Cu gas-diffusion electrode with the lowest Cu δ+ /Cu 0 ratio prefers C–C coupling to form C 2+ products with Faradaic efficiency topping 80.1% at -0.75 V vs RHE, where the Faradaic efficiency of C 2 H 4 accounts for 46.4% and the partial current density of C 2 H 4 achieves 279 mA cm -2 . This work demonstrates that the selectivity from CH 4 to C 2 H 4 is switchable by tuning surface Cu species composition of Cu gas-diffusion electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A pyrolysis study of allylic hydrocarbon fuels

The pyrolysis of selected C 3 –C 5 allylic hydrocarbons has been studied using a single-pulse shock tube. A new single-pulse shock tube has been designed and constructed by recommissioning an existing conventional shock tube. This facility enables the investigation of high-temperature chemical kinetics with an emphasis on combustion chemistry. The modifications performed on the existing shock tube are described, and the details of the sampling system to analyze the species concentration using a gas chromatography-mass spectrometry-flame ionization detection (GC-MS with a flame ionization detector) system are also provided. This facility is characterized and validated by performing cyclohexene pyrolysis experiments. Furthermore, the performance of the shock tube is demonstrated by reproducing previous literature measurements on the pyrolysis of isobutene. Postvalidation, this setup is used to study the pyrolysis of trans-2-butene and 2-methyl-2-butene (2M2B). A newly developed mechanism, NUIGMech1.0, is used to simulate the experimental data of propene, isobutene, 2-butene, and 2M2B, allylic hydrocarbon fuels. A description using two different kinetic simulation approaches is provided using our isobutene experiments as a reference. We found no significant differences between the two methods. Additionally, the contribution of different reaction classes on fuel consumption is detailed and the influence of geometry on fuel consumption and first aromatic ring: benzene is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrocatalytic Valorization into H2 and Hydrocarbons of an Aqueous Stream Derived from Hydrothermal Liquefaction

Electrocatalytic oxidation is an attractive process for valorizing the carbon and removal of nitrogen present in the aqueous waste streams at ambient conditions. Here, we evaluated the electrocatalytic oxidation as a function of applied potential over a commercial Pt electrode of aqueous waste stream generated via hydrothermal liquefaction. We validated the conversion of quantifiable carbon (e.g., carboxylic acids, alpha hydroxyacids, alcohols, ketones, amides) and unquantifiable carbon as well as nitrogen removal. The unquantifiable carbon was valorized to quantifiable short chain organic molecules (e.g., acetic). Model studies showed that carboxylic acids, alcohol and ketones converted following (non-) Kolbe chemistry. Amides and alpha hydroxyacids formed carboxylic acids that subsequently converted via (non-) Kolbe chemistry. Ammonia was oxidized into N2. The reaction rate varied for each molecule family with carboxylic acids and ammonia having the highest reaction rates. The main reaction products from the electrocatalytic oxidation at the anode were volatile, short chain hydrocarbons (i.e., olefins, paraffins) and CO generated via Kolbe chemistry, while H2 was generated at the cathode. The parallel denitrification, valorization of carbon, and H2 generation of the aqueous waste can replace and simplify the current unit operations used in a commercial hydrothermal liquefaction process. The high operation potential required to drive the electrocatalytic reaction is responsible for high operation costs; however, they can be either partially subsidized with sale of excess H2 at the current DOE goal of $2/kg H2. Thus, the present work shows how electrocatalytic oxidation can be used to valorize aqueous waste streams into volatile hydrocarbons and H2.

Electrocatalytic oxidation, Aqueous waste valoriza↗
DOE OSTI2021

Deactivation trends of Pd/SSZ-13 under the simultaneous presence of NO, CO, hydrocarbons and water for passive NO x adsorption

Pd-functionalized chabazite (Pd/SSZ-13) was evaluated for passive NO x adsorption (PNA) using low temperature combustion with diesel (LTC-D) reaction feed of the “United States Driving Research and Innovation for Vehicle efficiency and Energy sustainability” (U.S.DRIVE) protocol. Notably as per the protocol conditions, 12% O 2 + 6% CO 2 + 6% H 2 O was flown in all cases. NO-uptake studies in the presence of the LTC-D feed showed a systematic decline with (NO:Pd)molar changing from 0.5 to 0.4 after 10 trials. Control experiments showed more pronounced decline for NO + CO case, with appreciable intial (NO:Pd)molar value of 0.4 yet comparable-to-the-LTC-D-feed decline after 8 trials. CO-induced particle formation and larger extent of particle sintering was also evident from TEM analysis. Other controls did not exhibit trial-dependent deactivation as(NO:Pd)molar values were constant, at 0.3, 0.2, 0.5 and 0.2 for the NO, NO+H 2 , NO + unsaturated hydrocarbon (C 2 H 4 , C 3 H 6 ) and NO + saturated HC (C 3 H 8 , C 10 H 22 ) feeds respectively. In addition to these quantitative differences, desorption behaviors are qualitatively different. While only one major desorption event is observed for the full LTC-D, NO+ CO and NO+ unsaturated HC-controls, desorption occurs in two distinct stages for NO, NO + saturated HCs and initial-NO+H 2 trials. This arises due to inherent differences in Pd sites while exposed to these chemically distinct feeds. Furthermore, presence of reducing agents such as CO and unsaturated HCs in the feed result in almost complete elimination of lower, sub-200 °C desorption peak. The higher temperature desorption peaks, at > 300 °C is associated with NO strongly bound to ionic Pd sites and are prevalent under reducing conditions. Using DRIFTS also, three complexes leading to PNA are assigned, [O = N–Pd 2 +(OH)–Z], [O = N–Pd 2 +(Z2)] and [O = N–Pd 2 +(H 2 O)y–Z] with the latter being clearly observed upon water exposure. Pd/SSZ-13 showed higher hydrocarbon trapping than the SSZ-13 counterpart.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Determination of permeability for hydrocarbon release due to excavation-induced stress redistribution in rock salt

Due to a stress redistribution after the excavation of an underground tunnel for radioactive waste disposal, an Ed/DZ (excavation disturbed/damaged zone) will be generated in the near field of the opening, resulting in significant changes in the hydraulic and mechanical properties of the rock mass in the zone. Initially more or less randomly distributed hydrocarbons at grain boundaries in rock salt, which sometimes can only be observed with ultraviolet light, can then be mobilised and migrate at a potentially significant rate towards the excavation. Within the international cooperative project DECOVALEX 2019, the migration mechanism of such fluid inclusions in rock salt is being studied intensively. Specifically, a multi-scale modelling strategy has been developed. A macroscale coupled hydro-mechanical modelling of an underground excavation was performed to determine hydraulic and time-dependent deviatoric stress conditions, by taking into account the rock salt creep behaviour. Under the obtained macro-scale constraints, micro-scale modelling of a pathway dilation along halite grain boundaries was performed using different model strategies: a) coupled hydromechanical modelling with a consideration of hydraulic pressure-induced dilatant deformation, b) nonlinear dynamic model taking account of fluid migration, stress-dependent grain boundary wetting and shear-induced dilatancy of salt, and c) phase-field modelling of flow pathway propagation. The permeability increase resulting from the pathway dilation is estimated to be as high as two orders of magnitude. Based on the permeability determined, a series of pressure buildups measured from a borehole with a high hydrocarbon release rate, a total of 430 build-ups within a monitoring time of 938 days, can be simulated with a macro-scale compressible flow model accounting for different zones around the opening.

58 GEOSCIENCES↗