Viscous multicomponent-multiphase flow with application to axisymmetric jets of hydrogen.
Flow of dilute suspension of condensing and evaporating components of cryogenic hydrogen, dumped into atmosphere
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Flow of dilute suspension of condensing and evaporating components of cryogenic hydrogen, dumped into atmosphere
While bio-oil-derived fuels hold much promise as a replacement for petroleum, transformation of the highly oxygenated mixture has proven challenging. In particular, bio-oils are reactive and difficult to upgrade through catalytic pyrolysis. To reach a stabilized product capable of deep deoxygenation at elevated pressure and temperature, conversion or separation of reactive groups is required. This paper describes an electrochemical process for stabilization and upgrading of bio-oils prior to hydrotreating at high pressure and temperature. This electrolytic process uses a three-compartment cell designed to hydrogenate reactive carbonyl components while separating small acid molecules, such as acetic and formic acids, which act as catalysts for condensation reactions and consume hydrogen gas to produce low-value gases in hydrotreating. To avoid conductivity issues, electrodes are appended to anion- and cation-exchange membranes. The cell was tested using a mixed acetic acid and formic acid surrogate fed to the cathode compartment, where the decrease in the concentration followed the applied charge to the cell. Experiments performed using pine pyrolysis oil demonstrated a significant reduction in the total acid number (TAN), an increase in pH from 2.6 to over 4, and a modest reduction of the carbonyl concentration. Analysis showed the reduction in TAN was primarily due to removal of carboxylic compounds. Experiments observed a decrease in the reactive carbonyl (aldehydes and ketones) concentration that followed applied charge. The results with the newly devised reactor show promise for the electrochemical route for upgrading bio-oils, but significant improvements in TAN removal and carbonyl conversion are needed. Given the distributed nature of biomass, an electrochemical process paired with pyrolysis could be used to densify and stabilize an oil product near the source. The densified liquid could then be shipped to centralized refineries for final upgrading to fuel and/or chemical products.
The components, design, and operating characteristics of Ni-H2 cells batteries were improved. A separator development program was designed to develop a separator that is resistant to penetration by oxygen and loose active material from then nickel electrode, while retraining the required chemical and thermal stability, reservoir capability, and high ionic conductivity. The performance of the separators in terms of cell operating voltage was to at least match that of state-of-the-art separators while eliminating the separator problems. The separators were submitted to initial screening tests and those which successfully completed the tests were built into Ni-H2 cells for short term testing. The separators with the best performance are tested for long term performance and life.
The components, design, and operating characteristics of Ni-H2 cells and batteries were improved. A separator development program was designed to develop a separator that is resistant to penetration by oxygen and loose active material from the nickel electrode, while retaining the required chemical and thermal stability, reservoir capability, and high ionic conductivity. The performance of the separators in terms of cell operating voltage was to at least match that of state-of-the-art separators while eliminating the separator problems. The separators were submitted to initial screening tests and those which successfully completed the tests were built into Ni-H2 cells for short term testing. The separators with the best performance are tested for long term performance and life.
The technical highlights and accomplishments made at NASA LeRC in the development of the Space Station Freedom (SSF) propulsion system are discussed. The objectives are as follows: develop and characterize resistojet-thruster components and assemblies; develop and characterize hydrogen-oxygen thruster components; and conduct system trade studies. The research projects primarily characterize propulsion performance and life. Other tests include environmental impacts, such as exhaust gas profiles and electromagnetic interference. The technical activities that are highlighted are being conducted at LeRC within the Aerospace Technology and Space Station Freedom directorates. These activities include the following: derivation of design analysis models; trade studies of design options; propulsion system impact studies; and component testing for characterization and design verification.
The higher rate of component failure and downtime during initial operation in hydrogen stations is not well understood. The National Renewable Energy Laboratory (NREL) has been collecting failed components from retail and research hydrogen fueling stations in California and Colorado and analyzing them using an optical zoom and scanning electron microscope. The results show stainless steel metal particulate contamination. While it is difficult to definitively know the origin of the contaminants, a possible source of the metal particulates is improper tube cleaning practices. To understand the impact of different cleaning procedures, NREL performed an experiment to quantify the particulates introduced from newly cut tubes. The process of tube cutting, threading and beveling, which is performed most often during station fabrication, is shown to introduce metal contaminants and thus is an area that could benefit from improved cleaning practices. This paper shows how these particulates can be reduced, which could prevent station downtime and costly repair. These results are from the initial phase of a project in which NREL intends to further investigate the sources of particulate contamination in hydrogen stations.
Potential structural material problems that may be encountered in the three components of a hydrogen energy system - production, transmission/storage, and utilization - were identified. Hydrogen embrittlement, corrosion, oxidation, and erosion may occur during the production of hydrogen. Hydrogen embrittlement is of major concern during both transmission and utilization of hydrogen. Specific materials research and development programs necessary to support a hydrogen energy system are described.
Potential structural material problems that may be encountered in the three components of a hydrogen energy system - production, transmission/storage, and utilization - have been identified. Hydrogen embrittlement, corrosion, oxidation, and erosion may occur during the production of hydrogen. Hydrogen embrittlement is of major concern during both transmission and utilization of hydrogen. Specific materials research and development programs necessary to support a hydrogen energy system are described. An awareness of probable shortages of strategic materials has been maintained in these suggested programs.
Biomass fast pyrolysis integrated with bio-oil upgrading represents a very attractive approach for converting biomass to hydrocarbon transportation fuels. However, the thermal and chemical instability of bio-oils presents significant problems when they are being upgraded, and development of effective approaches for stabilizing bio-oils is critical to the success of the technology. Catalytic hydrogenation to remove reactive species in bio-oil has been considered as one of the most efficient ways to stabilize bio-oil. This paper provides a fundamental understanding of hydrogenation of actual bio-oils over a Ru/TiO2 catalyst under conditions relevant to practical bio-oil hydrotreating processes. Bio-oil feed stocks, bio-oils hydrogenated to different extents, and catalysts have been characterized to provide insights into the chemical and physical properties of these samples and to understand the correlation of the properties with the composition of the bio-oil and catalysts. The results indicated hydrogenation of various components of the bio-oil, including sugars, aldehydes, ketones, alkenes, aromatics, and carboxylic acids, over the Ru/TiO2 catalyst and 120 to 160oC. Hydrogenation of these species significantly changed the chemical and physical properties of the bio-oil and overall improved its thermal stability, especially by reducing the carbonyl content, which represented the content of the most reactive species (i.e., sugar, aldehydes, and ketones). The change of content of each component in response to increasing hydrogen additions suggests the following bio-oil hydrogenation reaction sequence: sugar conversion to sugar alcohols, followed by ketone and aldehyde conversion to alcohols, followed by alkene and aromatic hydrogenation, and then followed by carboxylic acid hydrogenation to alcohols. Hydrogenation of bio-oil samples with different sulfur contents or inorganic material contents suggested that sulfur poisoning of the reduced Ru metal catalysts was significant during hydrogenation; however, the inorganics at low concentrations had minimal impact at short times on stream, indicating that sulfur poisoning was the primary deactivation mode for the bio-oil hydrogenation catalyst. Reducing the sulfur content in bio-oil could significantly increase the lifetime of the hydrogenation catalyst used. The knowledge gained during this work will allow rational design of more effective catalysts and processes for stabilizing and upgrading bio-oils.
The roles of interaction between two catalyst components in CuO–ZnO–ZrO 2 –Al 2 O 3 (CZZA)/HZSM-5 bifunctional catalyst for dimethyl ether (DME) synthesis via carbon dioxide hydrogenation were investigated. It was found that CZZA catalyst showed excellent stability during methanol (MeOH) synthesis for 100 h, while there was a severe loss of catalytic activity in the bifunctional catalyst for DME synthesis. So, the effects of different degrees of intimacy of two catalyst components were studied for DME synthesis, including mixed and separated modes. For the mixed mode, the particle size of catalysts and the amount of reaction intermediates were proven to influence the catalyst deactivation. For the separated mode, the catalysts showed rapid deactivation within a short time. Various characterizations indicated that the remarkable deactivation of separated mode was mainly caused by the decrease of copper active centers (e.g., sintering and oxidation) and blockage of acid sites via increased coke deposition on HZSM-5.
Large-scale underground hydrogen storage (UHS) is a critical component in the emerging hydrogen economy. Knowledge of multiphase flow behavior involving hydrogen in storage reservoir formations is crucial to characterizing hydrogen transport properties and essential for the deliverability and storage operations of UHS. There are still many gaps in fully understanding hydrogen–methane–brine multiphase phase flow that require further investigation. In this work, H 2 and CH 4 were injected through brine-saturated sandstone cores using a tri-axial core holder system fitted with flow rate meters and pressure transducers, while the effluent gas concentrations were analyzed using an online micro gas chromatograph. Brine displacement, permeability, and gas breakthrough curves were measured. We studied the flow behavior of hydrogen and methane in sandstone cores through testing brine displacement by gas injection and comparing the hydrogen displacement of methane with the methane displacement of hydrogen. We also tested the differences between horizontal and vertical flow in brine displacement. The results showed that brine displacement was more efficient in a core with higher permeability and porosity, resulting in a higher initial gas saturation. A higher gas injection rate brought about faster gas breakthrough measured by pore volume and sharper concentration curves. Hydrogen did not exhibit abnormal flow in the sandstone when the flow was horizontal and downward vertical. Gas overriding was observed in brine displacements when the flow was horizontal, with hydrogen showing this behavior more profoundly compared to methane. Downward vertical gas injection induced higher efficiency brine displacement compared to horizontal displacement and resulted in a higher initial gas saturation in the sandstone cores. These findings address critical knowledge gaps regarding gas flow patterns and displacement behaviors during hydrogen injection and recovery phases in UHS facilities using methane as the cushion gas. The insights from this research offer valuable guidance for optimizing UHS systems, ensuring operational efficiency, and advancing sustainable energy solutions in alignment with decarbonization goals.
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NASA has advanced NASA HR-1 as a solution for liquid rocket engine components that operate in hydrogen rich environments using various AM techniques. The NASA HR-1 for AM applications was specifically formulated for high ductility in high pressure gaseous hydrogen environment in addition to high strength and low cycle fatigue (LCF) resistance. NASA HR-1 meets materials requirements for liquid rocket engine components, including good hydrogen resistance, high conductivity, good LCF performance, and high elongation and strength for components in medium heat flux environments. NASA has completed fabrication of several subscale and full-scale channel wall nozzles in LP-DED NASA HR-1 and completed hot-fire testing. This includes refinement of the process to produce thin-walls and various channel geometries to meet the requirements for channel wall nozzle applications. The main objective of this investigation is to better understand the effects of tensile test strain rate and specimen surface finish on the amount of tensile ductility degradation in high pressure gaseous hydrogen environments. Performing smooth tensile tests in high pressure hydrogen and nitrogen environments can serve as a rapid and economical screening method to determine the relative susceptibility of materials to HEE. This paper presents the tensile test results for LP-DED NASA HR-1 in hydrogen and details the material evaluation on the effects of strain rate and surface finish condition on surface cracking behavior and fracture characteristics. The resistance to HEE for LP-DED NASA HR-1 and the wrought alloy is compared under the same testing conditions. Loss of tensile ductility is quantified in terms of changes in elongation at failure in hydrogen to compare HEE susceptibility. The most suitable strain rate and specimen surface finish condition for future HEE screening testing at MSFC are recommended.
This publication includes 98 composite data products (CDPs) produced for next generation hydrogen stations, with data through the third quarter of 2019. These CDPs include data from retail stations only and represent the following analysis categories: deployment, safety, maintenance and reliability, performance, cost, utilization, hydrogen quality, and component energy.
This publication includes 102 composite data products (CDPs) produced for next generation hydrogen stations, with data through the second quarter of 2020. These CDPs include data from retail stations only and represent the following analysis categories: deployment, safety, maintenance and reliability, performance, cost, utilization, hydrogen quality, and component energy.
The thermodynamic stability and melting point of magnesium borohydride were probed under hydrogen pressures up to 1000 bar (100 MPa) and temperatures up to 400 °C. At 400 °C, Mg(BH4)2 was found to be chemically stable between 700 and 1000 bar H2, whereas under 350 bar H2 or lower pressures, the bulk material partially decomposed into MgH2 and MgB12H12. The melting point of solvent-free Mg(BH4)2 was estimated to be 367-375 °C, which was above previously reported values by 40-90 °C. Our results indicated that a high hydrogen backpressure is needed to prevent the decomposition of Mg(BH4)2 before measuring the melting point and that molten Mg(BH4)2 can exist as a stable liquid phase between 367 and 400 °C under hydrogen overpressures of 700 bar or above. The occurrence of a pure molten Mg(BH4)2 phase enabled efficient melt-infiltration of Mg(BH4)2 into the pores of porous templated carbons (CMK-3 and CMK-8) and graphene aerogels. Both transmission electron microscopy and small-angle X-ray scattering confirmed efficient incorporation of the borohydride into the carbon pores. The Mg(BH4)2@carbon samples exhibited comparable hydrogen capacities to bulk Mg(BH4)2 upon desorption up to 390 °C based on the mass of the active component; the onset of hydrogen release was reduced by 15-25 °C compared to the bulk. Importantly, melt-infiltration under hydrogen pressure was shown to be an efficient way to introduce metal borohydrides into the pores of carbon-based materials, helping to prevent particle agglomeration and formation of stable closo-polyborate byproducts.
Green hydrogen is emerging as one of the most promising alternatives to replace fossil fuels. While hydrogen gas has a good energy density by weight, its poor energy density by volume requires it to be stored under high pressure for commercial use. The hydrogen infrastructure developed to handle this high pressure hydrogen contains multiple components made of polymers as sealing agents. Although polymers do not react chemically with hydrogen gas, they undergo a mechanical failure when high pressure hydrogen gas is suddenly depressurized. This phenomenon known as 'rapid decompression failure' occurs due to the diffusion of hydrogen through polymer and getting trapped inside pre-existing cavities or voids. Here, in this paper, a continuum mechanics-based coupled diffusion-deformation-damage model was developed to predict the hydrogen distribution, stress distribution, and damage propagation inside the polymer while it undergoes rapid decompression failure. The polymer was modeled as a hyperelastic material because it represents the nonlinear material response observed in uniaxial tensile tests perfectly. The effects of hydrogen diffusivity, pre-existing cavity size, cavity location, applied hydrogen pressure, and depressurization rate on damage initiation were studied. It was found that the coefficient of diffusion plays an important role in damage initiation and damage was mostly concentrated in the inside areas rather than near the surface. Experiments were conducted with EPDM polymer which agreed well with the predicted trends using the given model. The effect of adding carbon black and silica filler particles and plasticizer to the pure EPDM polymer was also studied. It was found that damage during RDF decreases with the addition of fillers, but increases with the addition of the plasticizer. Finally, the damage evolution in the presence of two cavities was also studied, and was found that the interaction of stress fields around the cavities alters the damage occurring during RDF.
One of the key components of carbon dioxide-free hydrogen production is a robust and efficient non-precious metal catalyst for the hydrogen evolution reaction. We report that a hierarchical nanoporous copper-titanium bimetallic electrocatalyst is able to produce hydrogen from water under a mild overpotential at more than twice the rate of state-of-the- art carbon-supported platinum catalyst. Although both copper and titanium are known to be poor hydrogen evolution catalysts, the combination of these two elements creates unique copper-copper-titanium hollow sites, which have a hydrogen-binding energy very similar to that of platinum, resulting in an exceptional hydrogen evolution activity. Moreover, the hierarchical porosity of the nanoporous-copper titanium catalyst also contributes to its high hydrogen evolution activity, because it provides a large-surface area for electrocatalytic hydrogen evolution, and improves the mass transport properties. Moreover, the catalyst is self-supported, eliminating the overpotential associated with the catalyst/support interface.