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At least 721 records · Page 40

Hydrogen and Ammonia Blending With Natural Gas: Ignition Delay Times and Chemical Kinetic Model Validation at Gas Turbine Relevant Conditions

Abstract Ignition delay times from undiluted mixtures of natural gas (NG)/H2/Air and NG/NH3/Air were measured using a high-pressure shock tube at the University of Central Florida. The combustion temperatures were experimentally tested between 1000–1500 K near a constant pressure of 25 bar. As mentioned, mixtures were kept undiluted to replicate the same chemistry pathways seen in gas turbine combustion chambers. Recorded combustion pressures exceeded 200 bar due to the large energy release, hence why these were performed at the high-pressure shock tube facility. The data is compared to the predictions of the NUIGMech 1.1 mechanism for chemical kinetic model validation and refinement. An exceptional agreement was shown for stoichiometric conditions in all cases but strayed at lean and rich equivalence ratios, especially in the lower temperature regime of H2 addition and all temperature ranges of the baseline NG mixture. Hydrogen addition also decreased ignition delay times by nearly 90%, while NH3 fuel addition made no noticeable difference in ignition time. NG/NH3 exhibited similar chemistry to pure NG under the same conditions, which is shown in a sensitivity analysis. The reaction CH3 + O2 = CH3O + O is identified and suggested as a possible modification target to improve model performance. Increasing the robustness of chemical kinetic models via experimental validation will directly aid in designing next-generation combustion chambers for use in gas turbines, which in turn will greatly lower global emissions and reduce greenhouse effects.

Pierro, Michael↗

Development of metallic nuclear material purification process via simultaneous chlorination and volatilization

Here, a purification process involving simultaneous chlorination and volatilization is reported using aluminum, iron, gallium, and uranium separation from cerium metal as the demonstration system. Anhydrous Cl 2 gas was reacted with the metal after it had been converted to small particles of hydride at temperatures ranging from 523 to 973 K. Each of the impurities should form chlorides with relatively high saturated vapor pressures. The objective of the process was to volatilize these chlorides after first achieving near-complete conversion of the metals to hydride and then chlorides. Complete conversion of hydrides to chlorides could not be achieved using relatively low-grade (99.5%) Cl 2 . High decontamination factors for all of the metal impurities required near complete conversion to chloride. It was concluded that oxygen contamination of the feed gas stream likely limits the conversion to chlorides by forming oxides instead, which then limits the volatilization of contaminants. Uranium was particularly challenging to remove in experiments suspected of having high oxygen contamination in the feed gas stream. After switching to ultra-high purity (99.999%) Cl 2 , complete conversion to chlorides within the measurement error was possible for the entire temperature range studied. Decontamination factors for aluminum, iron, gallium, and uranium were found to have average values of 1.9, 9.8, 14, and 5, respectively, at 973 K. While the process was most extensively studied using a once-through gas flow, recycling unreacted Cl 2 gas succeeded at minimizing waste while still maintaining complete conversion and similar decontamination factors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energetics of oxidation and formation of uranium monocarbide

To enable better implementation of uranium monocarbide (UC) as an advanced nuclear fuel for future high-temperature reactors, it is essential to have a thorough knowledge of its thermal and thermodynamic properties under reactor operational conditions. In this work, we studied thermal bulk oxidation of UC by simultaneous thermal analysis consisting of thermogravimetric analysis – differential scanning calorimetry coupled with evolved gas mass spectrometry (TGA-DSC-MS), and we examined the thermodynamic stability of UC using high temperature oxide melt drop solution calorimetry. Further, in air, our studied UC sample (which contains ~5 mol% UO 2 ) was found to undergo a step-wise thermal oxidation process consisting of consecutive oxidations and thermal decomposition reactions: 0.95UC·0.05UO 2 → UO 3 ·0.29(C x O y ) + 0.66CO 2 → UO 3 ·0.20(C x O y ) + 0.09CO 2 → UO 3 ·0.03(C x O y ) + 0.17CO 2 → U 3 O 8 + 0.03CO 2 + 0.166O 2 . DSC was further used to determine the enthalpies of reactions associated with this series of oxidation reactions. Synchrotron X-ray diffraction (XRD) and extended X-ray absorption spectroscopy (EXAFS) were performed to characterize both the long- and short-range structures of UC. The standard enthalpy of formation (ΔH° f ) of UC was determined to be –50.7 ± 10.8 kJ/mol·atom, in good agreement with previous values measured by bomb calorimetry. Lastly, the enthalpic landscape of U-C compounds, including UC, U 2 C 3 , and α-UC 1.94 , were established based on the enthalpy normalized per mole atom, which suggests that U-C phases are thermodynamically stable at lower C/U ratios.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Process Intensification by One-Step, Plasma-Assisted Catalytic Synthesis of Liquid Chemicals from Light Hydrocarbons

In this project, we present a plasma-assisted, catalytic process that can handle variations in production rates and gas compositions of producing wells and reliably converts the hydrocarbons to gas phase olefins, high molecular weight alkanes, and liquid chemicals. The low-temperature plasma serves as a reactive chemical environment that activates and converts the light hydrocarbons to these valuable products. We present results from the integration of a catalyst into the low-temperature plasma zone to improve reaction efficiency and product selectivity. We show that the gas composition, bulk gas temperature, and input power of the plasma, with and without catalysts, influence the production rates of liquids from natural gas feeds.

03 NATURAL GAS↗

An improved semi-global intrinsic kinetics model for high temperature carbon oxidation

Measurements of the oxidation rates of various forms of carbon (soot, graphite, coal char) have often shown an unexplained attenuation with increasing temperatures in the vicinity of 2000 K, even when accounting for diffusional transport limitations and gas-phase chemical effects (e.g. CO 2 dissociation). With the development of oxy-fuel combustion approaches for pulverized coal utilization with carbon capture, high particle temperatures are readily achieved in sufficiently oxygen-enriched environments. Here, in this work, a new semi-global intrinsic kinetics model for high temperature carbon oxidation is created by starting with a previously developed 5-step mechanism that was shown to reproduce all major known trends in carbon oxidation, except for its high temperature kinetic falloff, and incorporating a recently discovered surface oxide decomposition step. The predictions of this new model are benchmarked by deploying the kinetic model in a steady-state reacting particle code (SKIPPY) and comparing the simulated results against a carefully measured set of pulverized coal char combustion temperature measurements over a wide range of oxygen concentrations in N 2 and CO 2 environments. The results show that the inclusion of the spontaneous surface oxide decomposition reaction step significantly improves predictions at high particle temperatures. Furthermore, the simulations reveal that O atoms released from the oxide decomposition step enhance the radical pool in the near-surface region and within the particle interior itself. Incorporation of literature rates for O and OH reactions with the carbon surface results in a reduction in the predicted radical pool concentrations and a very minor enhancement of the overall carbon oxidation rate.

33 ADVANCED PROPULSION SYSTEMS↗

High‐Throughput Computational Guided Development of Refractory Complex Concentrated Alloys‐based Composite

ULTIMATE is a leading-edge DOE program to develop ultrahigh temperature materials for gas turbine use in the aviation and power generation industries. This team, headquartered at West Virginia University and including collaborators from the National Energy Technology Laboratory and Advanced Manufacturing LLC, has developed a new class of ultra-high temperature Refractory Complex Concentrated Alloys-based Composites (RCCC) for high temperature applications such as combustion turbines used in the aerospace and energy industries. The RCCC consist of Refractory Complex Concentrated Alloys (RCCA) mixed with particles of Refractory High Entropy Carbides, to increase RCCA strength to withstand extreme conditions. These new materials optimize the balance among strength, creep (deformation), density, and stability at 1300 °C (2372 °F), while maintaining ductility once the alloy cools to room temperature. The research team has developed advanced manufacturing processes using the pulsed electric current and laser 3D printing to produce test coupons of these materials.

36 MATERIALS SCIENCE↗

High-density SSiC 3D-printed Lattices for Compact HTHP Aero-engine Recuperators

The proposed project utilizes advanced ceramic-based 3D-printing technology to develop light, low-cost, ultra-compact, high-temperature high-pressure (HTHP) heat exchangers (HX) for the harsh oxidizing environment of aircraft gas-turbine engines. Typical 3D printing technologies (powder bed or lithographic techniques) cannot produce large high-density, monolithic ceramic material with intricate internal features and channels required for high-temperature, high-pressure recuperators. Furthermore, typical 3D printing technologies are not yet economical for large high-density components. A high-density material is required for hermeticity, high-temperature strength, and oxidation, corrosion, and wear resistance. The team has invented an extrusion-based additive manufacturing technology (referred to as robocasting) and developed processing techniques to tailor composition and rheological mix properties for rapid 3D printing of high-density alumina and SiC parts. The goal of the proposed project is to use robocasting technology to demonstrate commercializable high-density 3D-printed ceramic HX modules with high durability and quality, thereby reducing the risk of thermo-mechanical failure under extreme environments. In addition, the proposed project improves the quality of the ceramic 3D-printing process over a large printed area and HTHP operating conditions. Ceramic 3D printing technology also provides a means to create advanced topologies that are unobtainable with conventional manufacturing.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Abstract Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

25 ENERGY STORAGE↗

Revealing Sintering Kinetics of MoS 2 -Supported Metal Nanocatalysts in Atmospheric Gas Environments via Operando Transmission Electron Microscopy

The decoration of two-dimensional (2D) substrates with nanoparticles (NPs) serve as heterostructures for various catalysis applications. Deep understanding of catalyst degradation mechanisms during service conditions is crucial to improve the catalyst durability. In this work, we studied the sintering behavior of Pt and bimetallic Au-core Pt-shell (Au@Pt core–shell) NPs on MoS 2 supports at high temperatures under vacuum, nitrogen (N 2 ), hydrogen (H 2 ), and air environments by in situ gas-cell transmission electron microscopy (TEM). The key observations are summarized as effect of environment: while particle migration and coalescence (PMC) was the main mechanism that led to Pt and Au@Pt NPs degradation under vacuum, N 2 , and H 2 environments, the degradation of MoS 2 substrate was prominent under exposure to air at high temperatures. Pt NPs were less stable in H 2 environment when compared with the Pt NPs under vacuum or N 2 , due to Pt–H interactions that weakened the adhesion of Pt on MoS 2 . Effect of NP composition: under H 2 , the stability of Au@Pt NPs was higher in comparison to Pt NPs. This is because H 2 promotes the alloying of Pt–Au, thus reducing the number of Pt at the surface (reducing H 2 interactions) and increasing Pt atoms in contact with MoS 2 . Effect of NP size: The alloying effect promoted by H 2 was more pronounced in small size Au@Pt NPs resulting in their higher sintering resistance in comparison to large size Au@Pt NPs and similar size Pt NPs. The present work provides key insights into the parameters affecting the catalyst degradation mechanisms on 2D supports.

2D materials↗

Nanostructured, Targeted Layered Metal Oxides as Active and Selective Heterogeneous Electrocatalysts for Oxygen Evolution

Oxygen evolution reaction (OER) is an important chemical transformation that governs the performance of technologically relevant energy conversion and storage processes, such as electrochemical water splitting in electrolyzers and metal-air batteries. This reaction involves the evolution of oxygen gas from (i) oxygen ions formed from water splitting at high temperatures, (ii) oxygen containing species (i.e., OH, OOH) formed from water splitting at low temperatures, and (iii) metal-oxide discharge products (M x O 2 ) in metal-air batteries. One of the main challenges with OER is that it is catalyzed at low temperatures by noble metal-based electrocatalysts, which are expensive (making this process economically unviable), or at high temperatures by metal-oxide based electrocatalysts that are inefficient and lead to high overpotential losses. Our preliminary results, as well as other results in the literature, show that non-noble metal-based oxide electrocatalysts with layered structures, known as nickelate oxides, exhibit promising OER activity. Nickelate oxides (A 2 MO 4+δ ) belong to the Ruddlesden-Popper series composed of alternating perovskite-like and rocksalt-like layers. They are promising OER electrocatalysts due to their high oxygen transport/exchange properties compared to the state-of-the-art perovskite-type oxides. Unfortunately, these materials are fairly unexplored and little is known about the properties that govern their OER activity. Our preliminary studies, where we combine density functional theory (DFT) calculations, selective synthesis and characterization, show that engineering their nanocrystalline structure can significantly impact their catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges and successes in establishing a multipurpose fuels and materials irradiation capsule [Slides]

This presentation discusses the challenges and success related to designing and fabricating multipurpose capsules for irradiation experiments for irradiation within the Advanced Test Reactor (ATR) to be presented at tje DEVICE-MTR irradiation experiment design working group meeting hosted by the Japanese Atomic Energy Agency (JAEA). The information herein is limited to the design of the capsules only and no programmatic information from any project supporting the design of the multipurpose capsule is discussed. The intent of the design team was establish a capsule design that could accommodate multiple different irradiation project needs for the irradiation of nuclear fuel and materials of interest in the nuclear field. The main points of the presentation are as follows: use of tin as a molten thermal bond material was selected for the fueled capsule design and was found to be inadequate as it would corrode the stainless steel at high temperatures, this capsule design has high sensitivity to manufacturing of the gas gap and control of the gas mixture, and the fueled capsule has experienced welding challenges with the inner capsule material 800H Incoloy.

42 ENGINEERING↗

Cold spray chromium coating for nuclear fuel rods

A method is provided for coating the substrate of a component, such as a zirconium alloy cladding tube, for use in a water cooled nuclear reactor under normal operating conditions and under high temperature oxidation conditions. The method includes heating a pressurized carrier gas to a temperature between 200° C. and 1200° C., adding chromium or chromium-based alloy particles having an average diameter of 20 microns or less to the heated carrier gas, and spraying the carrier gas and particles onto the substrate at a velocity, preferably from 800 to 4000 ft./sec. (about 243.84 to 1219.20 meters/sec.), to form a chromium and/or chromium-based alloy coating on the substrate to a desired thickness.

36 MATERIALS SCIENCE↗

Gaseous hydrogen storage system with cryogenic supply

A gaseous hydrogen storage and distribution system with a cryogenic supply and a method for the cryogenic conversion of liquid hydrogen into high-pressure gaseous hydrogen are provided. The gaseous hydrogen storage and distribution system includes pressuring liquid hydrogen from a cryogenic tank using a low pressure liquid pump before vaporization within a relatively small vaporizer. The resulting high pressure gaseous hydrogen is transferred to a plurality of storage tanks at ambient temperature according to a desired fill sequence. The high pressure hydrogen gas is subsequently distributed from the storage tanks through a hydrogen fueling dispenser according to a desired dispensing sequence. The present system and method provide improvements in operational safety, eliminates the use of high pressure gas compressor, and minimizes boiling off and ventilation losses at a reduced cost when compared to existing thermal compression storage systems.

Feng, Zhili↗

AlGaN High Electron Mobility Transistor for High-Temperature Logic

Here we report on AlGaN high electron mobility transistor (HEMT)-based logic development, using combined enhancement- and depletion-mode transistors to fabricate inverters with operation from room temperature up to 500°C. Our development approach included: (a) characterizing temperature-dependent carrier transport for different AlGaN HEMT heterostructures, (b) developing a suitable gate metal scheme for use in high temperatures, and (c) over-temperature testing of discrete devices and inverters. Hall mobility data (from 30°C to 500°C) revealed the reference GaN-channel HEMT experienced a 6.9x reduction in mobility, whereas the AlGaN channel HEMTs experienced about a 3.1x reduction. Furthermore, a greater aluminum contrast between the barrier and channel enabled higher carrier densities in the two-dimensional electron gas for all temperatures. The combination of reduced variation in mobility with temperature and high sheet carrier concentration showed that an Al-rich AlGaN-channel HEMT with a high barrier-to-channel aluminum contrast is the best option for an extreme temperature HEMT design. Three gate metal stacks were selected for low resistivity, high melting point, low thermal expansion coefficient, and high expected barrier height. The impact of thermal cycling was examined through electrical characterization of samples measured before and after rapid thermal anneal. The 200-nm tungsten gate metallization was the top performer with minimal reduction in drain current, a slightly positive threshold voltage shift, and about an order of magnitude advantage over the other gates in on-to-off current ratio. After incorporating the tungsten gate metal stack in device fabrication, characterization of transistors and inverters from room temperature up to 500°C was performed. The enhancement-mode (e-mode) devices’ resistance started increasing at about 200°C, resulting in drain current degradation. This phenomenon was not observed in depletion-mode (d-mode) devices but highlights a challenge for inverters in an e-mode driver and d-mode load configuration.

42 ENGINEERING↗

Electron energy distributions in the extended gas nebulae associated with high-z AGN: Maxwell–Boltzmann versus κ distributions

ABSTRACT Emission line observations together with photoionization models provide important information about the ionization mechanisms, densities, temperatures, and metallicities in active galactic nuclei (AGN)-ionized gas. Photoionization models usually assume Maxwell–Boltzmann (M–B) electron energy distributions (EED), but it has been suggested that using κ distributions may be more appropriate and could potentially solve the discrepancies in temperatures and abundances found in HII regions and planetary nebulae. We consider the impact of the presence of κ distributions in photoionized nebulae associated with AGN and study how this might affect spectral modelling and abundance analyses for such regions. Using the photoionization code MAPPINGS 1e, we compute models adopting M–B and κ distributions of electron energies and compare the behaviour of emission line ratios for different values of κ, gas metallicity, density, ionization parameter, and SED slope. We find that the choice of EED can have a large impact on some UV and optical emission lines emitted by photoionized nebulae associated with AGN, and that the impact of adopting a κ distribution is strongly dependent on gas metallicity and ionization parameter. We compile a sample of line ratios for 143 type 2 AGN and compare our models against the observed line ratios. We find that for 98 objects, κ distributions provide a better fit to the observed line ratios than M–B distributions. In addition, we find that adopting κ-distributed electron energies results in significant changes in the inferred gas metallicity and ionization parameter in a significant fraction of objects.

Morais, S. G. (ORCID:0000000200927813)↗

Optimization of Operating Profit for the FEED of the PZAS Process for CO 2 Capture on a 460 MW NGCC

A rating model of PZAS (Piperazine with the Advanced Stripper) for a 460 MW natural gas combined cycle was developed from vendor-provided equipment performance data. Surrogate rating models were built and used to optimize variable profit of the system subject to natural gas and electricity price at a fixed value for CO 2 of $\$80$/tonne. Several process constraints were considered between ambient temperatures of 4.4 and 40.5 °C. Lower lean loading resulted in lower reboiler heat duty of about 2.2 GJ/tonne. Lean loading at 0.2 mol/equiv N was sufficient at an ambient temperature of 4.4 °C to maximize variable profit. Solvent precipitation was avoided even at low lean loading (0.18 mol/mol) in the absence of a trim cooler for the lean solvent between the absorber and the cold cross exchanger. Optimal CO 2 removal was always higher than the design case removal of 90% and achieved a peak of 93.6% for 4.4 ºC ambient temperature. Lean solvent rate was a significant driver of profitability. The maximum capacity of the compressor was a significant constraint on profitability. Increasing compressor capacity by 20–30% could increase variable profit by about 21% in the case of 0.18 lean loading at 4.4 °C ambient temperature. Furthermore, this increase in profit was lower at higher ambient temperature and higher lean loading. The breakeven gas price was $\$4.6$/MMBtu at high lean loading of 0.22 mol/mol. Below this value, profit was maximized by increasing the boiler heat rate. Above this value, profit could not be increased by burning additional natural gas, requiring a reduction in boiler heat rate and consequently, specific heat duty. At lower lean loading (0.2, 0.18 mol/mol), this transition in heat duty was not observed due to the lower heat duty. As the ambient temperature increased, a similar trend in heat duty was observed at 0.22 lean loading, but the transition to lower heat duty occurred earlier at $\$4$/MMBtu. This was because of the lower CO 2 production at higher ambient temperature, making the process unprofitable at a gas price higher than $\$3$/MMBtu unless the heat duty of the stripper and natural gas boiler is steeply decreased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗