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At least 145 records · Page 8

Energy storage using an REP with an engine

An energy storage system includes a power plant configured to generate an exhaust gas comprising carbon dioxide. The energy storage system further includes a first fuel cell configured to operate in reverse as an electrolyzer. The first fuel cell is configured to receive at least a portion of the exhaust gas from the power plant. An anode is configured to receive carbon dioxide via the exhaust gas and methane from a separate feed, and the anode is configured to output a hydrogen-containing gas mixture. The energy storage system further includes a reformer configured to methanate the hydrogen-containing gas mixture to convert substantially all of the carbon monoxide in the hydrogen-containing gas mixture to methane. The energy storage system further includes a second fuel cell operating in reverse as a hydrogen pump, the second fuel cell configured to separate hydrogen from a gas mixture output by the reformer.

25 ENERGY STORAGE↗

Assembly of the MOLLER Toroidal Magnets at Jefferson Lab

The MOLLER experiment at the Thomas Jefferson National Accelerator Facility (JLab) aims to precisely measure the weak interaction between electrons. This experiment leverages the 12 GeV electron beam and will run for three years. A crucial component of MOLLER is a system of five uniquely shaped water-cooled toroidal magnets. These magnets, possessing seven-fold symmetry, are designed to focus particles by separating electrons scattered off hydrogen in a liquid hydrogen target. The five magnets separate electrons scattered off electrons (Møller scattering) and protons (elastic e-p scattering) within target into approximately circular rings at the detector. Here, this paper presents the assembly process for these five toroidal magnets, detailing critical steps including epoxy application, pin insertion, soldering and brazing, coil assembly, and alignment, all performed to meet stringent magnet specifications. Additionally, it discusses challenges encountered during construction and highlights lessons learned, offering insights for future magnet development projects.

Lamont, Joseph [Thomas Jefferson National Accelera↗

Separator development and testing of nickel-hydrogen cells

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.

Gonzalez-Sanabria, O. D.↗

Separator development and testing of nickel-hydrogen cells

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.

Gonzalez-Sanabria, O. D.↗

Characteristic of cryogenic hydrogen flames from high-aspect ratio nozzles

Unintentional leaks at hydrogen fueling stations have the potential to form hydrogen jet flames, which pose a risk to people and infrastructure. The heat flux from these jet flames are often used to develop separation distances between hydrogen components and buildings, lot-lines, etc. The heat flux and visible flame length is well understood for releases from round nozzles, but real unintended leaks would be expected to be from higher aspect-ratio cracks. Here, we measured the visible flame length and heat-flux characteristics of cryogenic hydrogen flames from high-aspect ratio nozzles. Heat flux measurements from 5 radiometers were used to assess the single-point vs the multi-point methods for interpretation of heat flux sensor data, finding the axial distance of the sensor for a single-point heat flux measurement to be important. We compare the flame length and heat flux data to flames of both cryogenic and compressed hydrogen from round nozzles. The aspect ratio of the release does not affect the flame length or heat flux significantly, for a given mass flow under the range of conditions studied. The engineering correlations presented in this work enable the prediction of flame length and heat flux which can be used to assess risk at hydrogen fueling stations with liquid hydrogen and develop science-based separation distances for these stations.

08 HYDROGEN↗

Atomically Fine-Tuning Organic–Inorganic Carbon Molecular Sieve Membranes for Hydrogen Production

Polymeric membranes with great processability are attractive for the H 2 /CO 2 separation required for hydrogen production from renewable biomass with carbon capture for utilization and sequestration. However, it remains elusive to engineer polymer architectures to obtain desired sub-3.3 Å ultramicropores to efficiently sieve H 2 from CO 2 . Herein, we demonstrate a scalable way of carbonizing polybenzimidazole (PBI) at low temperatures, followed by vapor phase infiltration (VPI) to atomically narrow ultramicropores throughout the films, forming hybrid organic–inorganic carbon molecular sieves (CMSs). One VPI cycle (100 s) for the PBI carbonized at 500 °C remarkably increases H 2 /CO 2 selectivity from 9.6 to 83 at 100 °C, surpassing Robeson’s upper bound. The CMS demonstrates a stable H 2 /CO 2 separation performance when challenged with simulated syngas streams and can be fabricated into thin-film composite membranes, outperforming state-of-the-art membranes. Finally, the scalable approach can be ubiquitous to molecularly fine-tune ultramicropores of leading polymeric membranes to further improve their size-sieving ability and thus separation efficiency.

36 MATERIALS SCIENCE↗

Winter bulge and diurnal variations in hydrogen inferred from AE-C composition measurements

In situ mass spectrometric measurements of ion and neutral particle thermospheric compositions have been used to infer the latitudinal and diurnal variations of thermospheric atomic hydrogen for solstice conditions. Local time-dependent and local time-independent components of the observed hydrogen distribution were separated on the basis of a model generated by expanding the log of neutral hydrogen concentration in terms of spherical harmonics. Results are compared with analogous data on N2 concentration; the comparison reveals an anticorrelation between gas temperature and hydrogen concentration. The slope of this anticorrelation line represents the 'zero flux condition' from the exosphere theory of Hodges (1973), thus further bearing out the conclusion that exospheric flow is the dominant process governing the global distribution of hydrogen.

Brinton, H. C.↗

Methods for Estimating Hydrogen Fuel Tank Characteristics

The pressure vessels needed to store hydrogen for next-generation hydrogen fuel cell vehicles are expected to be a substantial portion of the total system mass, volume, and cost. Gravimetric capacity, volumetric capacity, and cost per kilogram of usable hydrogen are key performance metrics that the U.S. Department of Energy (DOE) uses to determine the viability of hydrogen fuel cell systems. Research and development related to hydrogen storage systems covers a wide range of potential operating conditions, from cryogenic temperatures to high temperatures (above ambient) and low pressure to high pressure. Researchers at PNNL have developed methods for estimating these key pressure vessel characteristics to support on-board hydrogen storage system design and performance evaluation and to support decision-making about DOE hydrogen storage system research investments. This article describes the pressure tank estimation methodology that has been used as a stand-alone calculation and has been incorporated into larger system evaluation tools. The methodology estimates the geometry, mass, and material cost of type I, type III, and type IV pressure vessels based on operating pressure and material strength at the system's operating temperature, using classical thin-wall and thick-wall pressure vessel stress calculations. The geometry, mass, and material cost requirements of the pressure vessel have significant impacts on the total system performance. For example, hydrogen storage materials that can separately achieve a very high hydrogen density can be deemed impractical for use in fuel cell vehicle hydrogen storage systems because the pressure tank containing them is too large, heavy, or expensive. This article describes the design philosophy and analytical process of the tank characteristic estimation methodology, which has been implemented in spreadsheet calculation tools and system-level analysis tools used by DOE researchers. Each of the three tank types (type I, type III, and type IV) uses a different analysis methodology with some common elements. This article also provides examples of implementing the methodology to perform parametric studies of all three pressure vessel types. The goal of this article is to present the methodology in sufficient detail so it can be implemented in other hydrogen fuel cell vehicle design and analysis tools.

42 ENGINEERING↗

Increased Oxygen Recovery from Sabatier Systems Using Plasma Pyrolysis Technology and Metal Hydride Separation

State-of-the-art life support carbon dioxide (CO2) reduction technology is based on the Sabatier reaction where less than 50% of the oxygen required for the crew is recovered from metabolic CO2. The reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by the limited availability of reactant hydrogen. This is further exacerbated when Sabatier methane (CH4) is vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover hydrogen has the potential to dramatically increase oxygen recovery and thus drastically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. Due to the highly unstable nature of acetylene, a separation system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of a full-scale Third Generation PPA is reported and investigations into metal hydride hydrogen separation technology is discussed.

Zachary W Greenwood↗

Finely tuning the microporosity in phosphoric acid doped triptycene-containing polybenzimidazole membranes for highly permselective helium and hydrogen recovery

High-performance polymer membranes with well-defined microporosity and size-sieving ability are especially attractive for helium and hydrogen recovery. Here, in this study, we report novel macromolecular engineering of polybenzimidazole (PBI) membranes that integrate hierarchical triptycene units for high permeability and polyprotic acid doping for size sieving via controllable manipulation of microporous architecture. The triptycene moieties disrupt chain packing and introduce additional configurational free volume, leading to significantly boosted He and H 2 permeabilities compared to previously reported PBI membranes. The acid doping resulted in crosslinked PBI membranes via hydrogen bonding and proton transfer with dramatically enhanced gas selectivities. Via adjusting the H 3 PO 4 -doping level, triptycene-based polybenzimidazole (TPBI) composite membranes (TPBI-(H 3 PO 4 ) x ) exhibit the highest gas selectivities for He enrichment (i.e., α(He/CH 4 ) = 7052 ± 156) and H 2 purification (i.e., α(H 2 /CH 4 ) = 5128 ± 110) among existing polymeric gas separation membranes. Additionally, under mixed-gas conditions at 150 °C, the TPBI-(H 3 PO 4 ) 0.98 membrane displays a H 2 permeability of 46.7 Barrer and a H 2 /CO 2 selectivity of 16, far beyond the Robeson's 2008 upper bound for H 2 /CO 2 separation. The facile and diverse tunability and excellent gas separation performance make TPBI-(H 3 PO 4 ) x membranes highly attractive for helium and hydrogen separation.

42 ENGINEERING↗

Hydrogen and helium velocities in the solar wind.

Examination of separately determined helium and hydrogen bulk speeds in the solar wind show these to be equal, both on time scales of 30 min and 3 min. Observations of two interplanetary shocks and 12 discontinuities show the changes in bulk speed across them to take place simultaneously for the two species. Observations made at times of high helium abundance following an interplanetary shock, and at times of observation of colliding streams in the plasma, confirm the conclusion that, if bulk speed differences between species occur, they do so very rarely.

Ogilvie, K. W.↗

Evaluation of a spacecraft nitrogen generator

A research and development program was successfully completed towards the development of a method of generating nitrogen for cabin leakage makeup aboard space vehicles. The nitrogen generation concept used liquid hydrazine as the stored form of nitrogen. This reduced tankage and expendables weight associated with high pressure gaseous and cryogenic liquid nitrogen storage. The hydrazine was catalytically dissociated to yield a mixture of nitrogen and hydrogen. The latter was separated to provide the makeup nitrogen. The hydrogen will be used in the reduction of metabolic carbon dioxide.

Marshall, R. D.↗

Effect of storable propellants on single-stage earth-to-orbit vehicles

A comparison is made between the storable-propellant engine and an equivalent dual-expander engine using oxygen, propane, and hydrogen propellants. The propane and hydrogen dual-expander engine is then compared with previous results with separate propane and hydrocarbon engines. It is shown that the dual-expander reduces vehicle dry mass from 94 to 89 Mg, or 5%. The hydrogen-only thrust of the dual-expander is 0.4 MN, while the separate hydrogen engines have a thrust of 2.3 MN. The low thrust level increases the difficulty of cooling the dual-expander engine, and additional hydrogen flow is added for transpirational cooling. This additional hydrogen flow leads to an increase in the hydrogen tank size. It is also shown that storable propellants increase the dry mass of single-stage earth-to-orbit vehicles by about 20% and the gross mass by about 54%. It is concluded that dual-expander engines should be studied with several thrust splits and thrust levels.

Martin, J. A.↗

Exploring the Photophysics of N-Type Polymer N2200

The polymer interphase is a complex environment comprised of polymer chains, solvent molecules, and electrolyte ions. However, the microenvironments that these ingredients produce is both poorly-understood and difficult to investigate given the system's inherent structural heterogeneity. Nonetheless, a fundamental understanding of the structure, electrochemical behavior, and excited-state dynamics is a key prerequisite to optimizing devices based on such a system - for instance, photoelectrochemical cells for the direct, light-driven production of solar hydrogen, which may minimize efficiency losses compared to sequential light harvesting and electrochemical hydrogen production in separate but linked devices. This work combines transient absorption (TA) spectroscopy, which is a powerful tool for the observation of a variety of excited states on a femto- to microsecond timescale, with time-resolved microwave conductivity (TRMC) spectroscopy, which selectively probes the dynamics of free charge carriers (FC), of a blend of a donor polymer (PTB7-Th) and acceptor polymer (N2200) in a bulk heterojunction. Initial results indicate an extension of FC lifetime and homogenization of the microenvironment on a whole-film level, not just at the surface of the polymer; however, many questions are still under active investigation, including the changes in energy of the involved polaron states, effective conjugation length, FC mobility and migration distance, etc. Additional experiments regarding the photoinitiated behavior of the blend in different environments and on different timescales are ongoing.

charge recombination↗

Porous Organic Cages CC3 and CC2 as Adsorbents for the Separation of Carbon Dioxide from Nitrogen and Hydrogen

The selective capture of carbon dioxide over nitrogen and hydrogen is of great industrial interest in flue gas and hydrogen purification respectively. Microporous adsorbents are highly suitable materials to preferentially adsorb gases. Here, in particular, Porous organic cages (POCs) with tunable hierarchically ordered micropores, high surface area, and thermodynamic affinity for CO 2 make them appealing candidates for these applications. Herein, we demonstrate that two prototypical POCs denoted as CC3, and CC2 with limiting pore aperture of 3.6 Å can selectively separate CO 2 from N 2 , and H 2 . For CC3 adsorption selectivities as high as ~ 8 and ~20 for CO 2 /N 2 and CO 2 /H 2 respectively were observed. For CC2 adsorption selectivities as high as ~ 9 and ~35 for CO 2 /N 2 and CO 2 /H 2 respectively were observed. Interestingly, the adsorption selectivity of the studied gases correlated linearly with polarizability selectivity.

Carbon Dioxide↗

Metal–Organic Framework Based Hydrogen-Bonding Nanotrap for Efficient Acetylene Storage and Separation

The removal of carbon dioxide (CO 2 ) from acetylene (C 2 H 2 ) is a critical industrial process for manufacturing high purity C 2 H 2 . However, it remains challenging to address the trade-off between adsorption capacity and selectivity, on account of their similar physical properties and molecular sizes. To overcome this difficulty, here we report a novel strategy involving the regulation of hydrogen-bonding nanotrap on the pore surface to promote the separation of C 2 H 2 /CO 2 mixtures, in three isostructural metal-organic frameworks (MOFs, named as MIL-160, CAU-10H, and CAU-23, respectively). Among them, MIL-160, which has abundant hydrogen-bonding acceptors as nanotraps, can selectively capture acetylene molecules and demonstrates ultra-high C 2 H 2 storage capacity (191 cm 3 g –1 , or 213 cm 3 cm –3 ) but much less CO 2 uptake (90 cm 3 g –1 ) under ambient conditions. The C 2 H 2 adsorption amount of MIL-160 is remarkably higher than the other two isostructural MOFs (86 cm 3 g –1 and 119 cm 3 g –1 for CAU-10H and CAU-23 respectively) under the same conditions. More importantly, both simulation and experimental breakthrough results show that MIL-160 sets a new benchmark for equimolar C 2 H 2 /CO 2 separation in terms of the separation potential (Δq break = 5.02 mol/kg) and C 2 H 2 productivity (6.8 mol/kg). In addition, in-situ FT-IR experiments combined with computational modeling further reveal that the unique host-guest multiple hydrogen-bonding interactions between the nanotrap and C 2 H 2 is the key factor for achieving extraordinary acetylene storage capacity and superior C 2 H 2 /CO 2 selectivity. Furthermore, this work provides a novel and powerful approach to address the trade-off of this extremely challenging gas separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and computational kinetics study of the liquid-phase hydrogenation of C=C and C=O bonds

Solvent effects on adsorption equilibrium and reaction kinetics are evaluated for hydrogenation reactions catalyzed by Pd/alumina in a series of different solvents. Three reactants – cyclohexene, benzene and benzaldehyde – and three solvents – n-heptane (HEP), methylcyclohexane (MCHA), decalin (DL) – have been investigated. Kinetic analysis of hydrogenation of cyclohexene reveals that hydrogen adsorbs on different sites from those where cyclohexene and the solvents adsorb; however, the presence of hydrogen on these separate sites affects the heats of adsorption of the hydrocarbons. When the solvent is a weakly interacting linear alkane (HEP), the rate determining step of the reaction is the first hydrogenation of adsorbed cyclohexene. Furthermore, this conclusion is supported by DFT calculations that show a higher enthalpy barrier for the first hydrogenation than for the second, while statistical thermodynamics analysis validates the physical significance of the entropy of adsorption parameters derived from the kinetic fitting of experimental data. By contrast, with solvents such as MCHA and DL, which interact more strongly with the metal surface and compete for active sites with the reactant and the surface intermediate, the rate limiting step seems to shift to the second hydrogenation step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photocatalytic generation of hydrogen from water

A concept designed to overcome the problems encountered when using photodissociation for the generation of hydrogen is discussed. The problems limiting the efficiency of photodissociation of water are the separation of the photolysis products and the high energy photons necessary for the reaction. It is shown that the dissociation energy of a large number of molecules is catalytically reduced when these molecules are in intimate contact with the surface of certain metals. It is proposed to develop a surface which will take advantage of this catalytic shift in dissociation energies to reduce the photon energy required to produce hydrogen. This same catalytic surface can be used to separate the reaction products if it is made so that one of the dissociations products is soluble in the metal and others are not. This condition is met by many metal systems such as platinum group metals which have been used commercially to separate hydrogen from other gases and liquids.

Bottoms, W. R.↗