Slush hydrogen production, storage, and distribution study program Final report, 4 Nov. 1965 - 29 Apr. 1966
Production of slush hydrogen for nuclear rocket propulsion testing
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Hypersonic Propulsion at Pratt and Whitney: Overview
Pratt & Whitney (P&W) is developing the technology for hypersonic components and engines. A supersonic combustion ramjet (scramjet) database was developed during the National Aero Space Plane (NASP) program using hydrogen fueled propulsion systems for space access vehicles and serves as a point of departure for the current emphasis on hydrocarbon scramjets. The Air Force Hypersonic Technology (HyTech) Office has put programs in place to develop the technologies necessary to demonstrate the operability, performance and structural durability of a liquid hydrocarbon fueled scramjet system that operates from Mach 4 to 8. Fuel-cooled superalloys and lightweight structures are being developed to improve thermal protection and durability and to reduce propulsion system weight. The application of scramjet engine technology as part of combined cycle propulsion systems is also being pursued under NASA and U.S. Air Force sponsorship. The combination of scramjet power and solid rocket booster acceleration is applicable to hypersonic cruise missiles. Scramjets that use gas turbines for low speed acceleration and scramjets using rocket power for low speed acceleration are being studied for application to reusable launch systems and hypersonic cruise vehicles. P&W's recent activities and future plans for hypersonic propulsion will be described.
Kazmar, Richard R.↗
Modified Ni-Cu catalysts for ethanol steam reforming
Three Ni-Cu catalysts, having different Cu content, supported on γ-alumina were synthesized by wet co-impregnation method, characterized and tested in the ethanol steam reforming (ESR) reaction. The catalysts were characterized for determination of: total surface area and porosity (N{sub 2} adsorption - desorption using BET and Dollimer Heal methods), Ni surface area (hydrogen chemisorption), crystallinity and Ni crystallites size (X-Ray Diffraction), type of catalytic active centers (Hydrogen Temperature Programmed Reduction). Total surface area and Ni crystallites size are not significantly influenced by the addition of Cu, while Ni surface area is drastically diminished by increasing of Cu concentration. Steam reforming experiments were performed at atmospheric pressure, temperature range 150-350°C, and ethanol - water molar ration of 1 at 30, using Ar as carrier gas. Ethanol conversion and hydrogen production increase by the addition of Cu. At 350°C there is a direct connection between hydrogen production and Cu concentration. Catalysts deactivation in 24h time on stream was studied by Transmission Electron Microscopy (TEM) and temperature-programmed reduction (TPR) on used catalysts. Coke deposition was observed at all studied temperatures; at 150°C amorphous carbon was evidenced, while at 350°C crystalline, filamentous carbon is formed.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chemical Grafting of Highly Dispersed VO x /CeO 2 for Increased Catalytic Activity in Methanol Oxidative Dehydrogenation
Vanadia supported on well-defned ceria nanocubes are synthesized at various loadings using a liquid-phase chemical grafting technique and are compared to those prepared using traditional incipient wetness impregnation. Raman and IR characterization reveal that, as vanadia loading is increased to near monolayer coverage, vanadia deposited using grafting shows greatly enhanced dispersion (i.e., improved VO x monomer/dimer distribution). Methanol is used as a probe molecule to explore the redox behavior of the catalysts. IR and temperature programmed desorption of methanol show increased CO 2 formation occurs on the bare ceria support and increasing the dispersion of vanadia promotes dehydrogenation to formaldehyde due to the inhibited oxygen vacancy formation on VO x /CeO 2 . Hydrogen temperature programmed reduction demonstrates that the catalyst reducibility and formation of surface oxygen vacancy are directly related to the degree of vanadia oligomerization. In conclusion, the samples prepared using grafting exhibit superior catalytic performance for methanol oxidative dehydrogenation to formaldehyde compared to the impregnated samples, due to the presence of highly dispersed VO x species (i.e., monomers and dimers).
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fractional Consumption of Liquid Hydrogen and Liquid Oxygen During the Space Shuttle Program
The Space Shuttle uses the propellants, liquid hydrogen and liquid oxygen, to meet part of the propulsion requirements from ground to orbit. The Kennedy Space Center procured over 25 million kilograms of liquid hydrogen and over 250 million kilograms of liquid oxygen during the 3D-year Space Shuttle Program. Because of the cryogenic nature of the propellants, approximately 55% of the total purchased liquid hydrogen and 30% of the total purchased liquid oxygen were used in the Space Shuttle Main Engines. The balance of the propellants were vaporized during operations for various purposes. This paper dissects the total consumption of liqUid hydrogen and liqUid oxygen and determines the fraction attributable to each of the various processing and launch operations that occurred during the entire Space Shuttle Program at the Kennedy Space Center.
Partridge, Jonathan K.↗
A study of hydrogen slush and/or hydrogen gel utilization. Volume 2 - Test program 41.5-inch diameter tank Final report
Subscale tank test evaluation of slush hydrogen technology for space vehicles
Source record↗
Development of a Micro-Fiber Nickel Electrode for Nickel-Hydrogen Cell
The development of a high specific energy battery is one of the objectives of the lightweight nickel-hydrogen (NiH2) program at the NASA Lewis Research Center. The approach has been to improve the nickel electrode by continuing combined in-house and contract efforts to develop a more efficient and lighter weight electrode for the nickel-hydrogen fuel cell. Small fiber diameter nickel plaques are used as conductive supports for the nickel hydroxide active material. These plaques are commercial products and have an advantage of increased surface area available for the deposition of active materials. Initial tests include activation and capacity measurements at different discharge levels followed by half-cell cycle testing at 80 percent depth-of-discharge in a low Earth orbit regime. The electrodes that pass the initial tests are life cycle tested in a boiler plate nickel-hydrogen cell before flightweight designs are built and tested.
Britton, Doris L.↗
CRADA Final Report For CRADA NO. CR-12-006 [Operation and Testing of an SO 2 -depolarized Electrolyzer (SDE) for the Purpose of Hydrogen and Sulfuric Acid Production]
Over the past several years, Savannah River National Laboratory (SRNL) has led a team of collaborators under the Department of Energy’s (DOE) nuclear hydrogen production program to develop the Hybrid Sulfur (HyS) Process. HyS is a 2-step water-splitting process consisting of high temperature decomposition of sulfuric acid to generate SO 2 , followed by the electrolysis of aqueous SO 2 to generate hydrogen and sulfuric acid. The latter is fed back into the high temperature reactor. SRNL designed and built an SO 2 -depolarized electrolyzer (SDE) and a test facility. Over 40 SDE’s were tested using different catalysts, membranes and other components. SRNL demonstrated that an SDE could be operated continuously for approximately 200 hours under certain conditions without buildup of sulfur at the SDE’s cathode, thus solving a key technical problem with SDE technology. Air Products and Chemicals, Inc. (APCI) is a major supplier of hydrogen production systems, and they have proprietary technology that could benefit from the SDE developed by SRNS, or some improved version thereof. However, to demonstrate that SRNL’s SDE is a truly viable approach to the electrolyzer design, continuous operation for far greater periods of time than 200 hours must be demonstrated, and the electrolyzer must be scaled up to greater hydrogen production capacities. SRNL and Air Products entered into a Cooperative Research and Development Agreement with the objective of demonstrating the effectiveness of the SDE for hydrogen and sulfuric acid production and to demonstrate long-term continuous operation so as to dramatically increase the confidence in the SDE design for commercial operation. SRNL prepared a detailed technical report documenting previous SDE development, including the current SDE design and operating conditions that led to the 200-hour sulfurfree testing. SRNL refurbished its single cell SDE test facility and qualified the equipment for continuous operation. A new membrane electrode assembly (MEA) was fabricated and installed in the single cell electrolyzer (60 cm 2 active cell area). Shakedown testing was conducted, and several modifications were made to the test facility equipment. Seven different MEAs were used during testing. Beginning on May 20, 2013, SRNL was able to test the SDE continuously for 1200 hours, including 1000 hours under power to generate hydrogen at an average rate of 10.8 liters per hour. The SDE was not removed or repaired during the 50-day test and was successfully restarted after each shutdown. The test was intentionally stopped after 1200 hours (1000 hours of hydrogen production) due to funding constraints. Post-test examination of the MEA using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Microanalysis (EDAX) showed no elemental sulfur deposits or sulfur layer inside the cell, thus successfully achieving the test goals. The results demonstrated that the SDE could be operated for extended periods without major performance degradation or the buildup of sulfur inside the MEA. Air Products conducted an assessment of the economic viability of the SDE based on the “as tested” design. The results indicated that the SDE faces significant economic obstacles in its current state. Further development and scale-up are necessary before the SDE is ready for commercialization.
08 HYDROGEN↗
Macro-System Model for Hydrogen Energy Systems Analysis in Transportation: Preprint
The Hydrogen Macro System Model (MSM) is a simulation tool that links existing and emerging hydrogen-related models to perform rapid, cross-cutting analysis. It allows analysis of the economics, primary energy-source requirements, and emissions of hydrogen production and delivery pathways.
08 HYDROGEN↗
Nickel-Hydrogen Battery Cell Life Test Program Update for the International Space Station
NASA and Boeing North America are responsible for constructing the electrical power system for the International Space Station (ISS), which circles the Earth every 90 minutes in a low Earth orbit (LEO). For approximately 55 minutes of this orbit, the ISS is in sunlight, and for the remaining 35 minutes, the ISS is in the Earth s shadow (eclipse). The electrical power system must not only provide power during the sunlight portion by means of the solar arrays, but also store energy for use during the eclipse. Nickel-hydrogen (Ni/H2) battery cells were selected as the energy storage systems for ISS. Each battery Orbital Replacement Unit (ORU) comprises 38 individual series-connected Ni/H2 battery cells, and there are 48 battery ORU s on the ISS. On the basis of a limited Ni/H2 LEO data base on life and performance characteristics, the NASA Glenn Research Center at Lewis Field commenced testing through two test programs: one in-house and one at the Naval Surface Warfare Center in Crane, Indiana.
Miller, Thomas B.↗
Development of a Renewable Hydrogen Production and Fuel Cell Education Program
This report presents the results of a program designed to develop an education program to 1) Provide exposure to the basics of hydrogen-based technologies to a large number of students. This exposure will provide a level of training that will allow students to converse and work with other scientists and engineers in this field. It will also serve to spark a level of interest in a subset of students who will then continue with more advanced coursework and/or research; 2) Provide a “mid-level” training to a moderate level of students. More detailed and directed education will provide students with the ability to work to support industry and government development of hydrogen technologies. This level of training would be sufficient to work in the industry, but not be a leader in research and development; and 3) Provide detailed training to a smaller subset of students with a strong interest and propensity to make significant contributions to the technology development. These individuals will have extensive hands-on experience through internships that will play a major role in industry, government, and academia.
08 HYDROGEN↗
Standardized Testing Program for Solid-State Hydrogen Storage Technologies
In the US and abroad, major research and development initiatives toward establishing a hydrogen-based transportation infrastructure have been undertaken, encompassing key technological challenges in hydrogen production and delivery, fuel cells, and hydrogen storage. However, the principal obstacle to the implementation of a safe, low-pressure hydrogen fueling system for fuel-cell powered vehicles remains storage under conditions of near-ambient temperature and moderate pressure. The choices for viable hydrogen storage systems at the present time are limited to compressed gas storage tanks, cryogenic liquid hydrogen storage tanks, chemical hydrogen storage, and hydrogen absorbed or adsorbed in a solid-state material (a.k.a. solid-state storage). Solid-state hydrogen storage may offer overriding benefits in terms of storage capacity, kinetics and, most importantly, safety. The fervor among the research community to develop novel storage materials had, in many instances, the unfortunate consequence of making erroneous, if not wild, claims on the reported storage capacities achievable in such materials, to the extent that the potential viability of emerging materials was difficult to assess. This problem led to a widespread need to establish a capability to accurately and independently assess the storage behavior of a wide array of different classes of solid-state storage materials, employing qualified methods, thus allowing development efforts to focus on those materials that showed the most promise. However, standard guidelines, dedicated facilities, or certification programs specifically aimed at testing and assessing the performance, safety, and life cycle of these emergent materials had not been established. To address the stated need, the Testing Laboratory for Solid-State Hydrogen Storage Technologies was commissioned as a national-level focal point for evaluating new materials emerging from the designated Materials Centers of Excellence (MCoE) according to established and qualified standards. Working with industry, academia, and the U.S. government, SwRI set out to develop an accepted set of evaluation standards and analytical methodologies. Critical measurements of hydrogen sorption properties in the Laboratory have been based on three analytical capabilities: 1) a high-pressure Sievert-type volumetric analyzer, modified to improve low-temperature isothermal analyses of physisorption materials and permit in situ mass spectroscopic analysis of the sample’s gas space; 2) a static, high-pressure thermogravimetric analyzer employing an advanced magnetic suspension electro-balance, glove-box containment, and capillary interface for in situ mass spectroscopic analysis of the sample’s gas space; and 3) a Laser-induced Thermal Desorption Mass Spectrometer (LTDMS) system for high thermal-resolution desorption and mechanistic analyses. The Laboratory has played an important role in down-selecting materials and systems that have emerged from the MCoEs.
08 HYDROGEN↗
Simulated Temperature Programmed Desorption of Acetaldehyde on CeO 2 (111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer
The temperature programmed desorption of acetaldehyde adsorbed on partially reduced CeO 2 (111) has been studied in detail using microkinetic modeling based on self-consistent, periodic density functional theory calculations at the GGA-PW91+U level. Previous experimental studies (Chen et al. J. Phys. Chem. C 115: 3385, 2011; Calaza et al. J. Am. Chem. Soc. 134: 18034, 2012) have shown that, whereas on fully oxidized CeO 2 (111) acetaldehyde desorbs molecularly with a peak temperature of 210 K, the polymerization and enolization of acetaldehyde dominate the surface reactivity on partially reduced CeO 2 (111), resulting in acetaldehyde desorption at higher temperatures. Here we propose a comprehensive reaction mechanism that is consistent with the spectroscopic evidence of the identities of the surface intermediates and with the observed desorption activities, including the formation of ethylene and acetylene. Besides acetaldehyde (CH 3 CHO) and its enolate (CH 2 CHO), several other C 2 H x O species are proposed as key intermediates which are not seen spectroscopically, including ethoxy (CH 3 CH 2 O), ethyleneoxy (CH2CH2O), and formylmethylene (CHCHO). Our study suggests that oxygen vacancies play the critical role of activating the carbonyl bond and thereby facilitating b C–H bond scissions in acetaldehyde, leading to enolization, intermolecular hydrogen transfer, deoxygenation, and potentially C–C coupling reactions.
Zhao, Chuanlin↗
Ultra-thin ZrO 2 overcoating on CuO-ZnO-Al 2 O 3 catalyst by atomic layer deposition for improved catalytic performance of CO 2 hydrogenation to dimethyl ether
Abstract An ultra-thin overcoating of zirconium oxide (ZrO 2 ) film on CuO-ZnO-Al 2 O 3 (CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO 2 to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO 2 ALD with HZSM-5 catalyst. All the catalysts modified by ZrO 2 ALD displayed significantly improved catalytic stability of hydrogenation of CO 2 to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO 2 ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Space Station Freedom NiH2 cell testing program
Testing for the Space Station Freedom Nickel Hydrogen Cell Test Program began in 1990 at Crave Division, Naval Surface Warfare Center. The program has included receipt inspection, random vibration, acceptance, characterization, and life cycle testing of Ni-H2 cells in accordance with the NASA LeRC Interagency Order C-31001-J. A total of 400 Ni-H2 cells have been received at NAVSURFWARCENDIV Crane from three separate manufacturers; Yardney Technical Products (Yardney), Eagle Picher Industries (Eagle Picher), and Gates Energy Products (Gates). Of those, 308 cells distributed among 39 packs have undergone life cycle testing under a test regime simulating low earth orbit conditions. As of 30 September 1993, there are 252 cells assembled into 32 packs still on life cycle test. Since the beginning of the program, failed cells have been detected in all phases of testing. The failures include the following; seven 65 AmpHr and 81 AmpHr Yardney cells were found to be leaking KOH on receipt, one 65 AmpHr Eagle Picher cell failed the acceptance test, one 65 AmpHr Gates cell failed during the characterization test, and six 65 AmpHr Gates cells failed the random vibration test. Of the 39 life cycle packs, testing on seven packs, 56 cells, has been suspended because of low end of discharge voltages. All of the failed life cycle packs were cycled at 60% depth of discharge.
Moore, Bruce↗
Elimination Of Catalytic Hydrogen Generation In Defense Waste Processing Facility Slurries
Based on lab-scale simulations of Defense Waste Processing Facility (DWPF) slurry chemistry, the addition of sodium nitrite and sodium hydroxide to waste slurries at concentrations sufficient to take the aqueous phase into the alkaline region (pH > 7) with approximately 500 mg nitrite ion/kg slurry (assuming <25 wt% total solids, or equivalently 2,000 mg nitrite/kg total solids) is sufficient to effectively deactivate the noble metal catalysts at temperatures between room temperature and boiling. This is a potential strategy for eliminating catalytic hydrogen generation from the list of concerns for sludge carried over into the DWPF Slurry Mix Evaporator Condensate Tank (SMECT) or Recycle Collection Tank (RCT). These conclusions are drawn in large part from the various phases of the DWPF catalytic hydrogen generation program conducted between 2005 and 2009. The findings could apply to various situations, including a solids carry-over from either the Sludge Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) into the SMECT with subsequent transfer to the RCT, as well as a spill of formic acid into the sump system and transfer into an RCT that already contains sludge solids. There are other potential mitigating factors for the SMECT and RCT, since these vessels are typically operated at temperatures close to the minimum temperatures that catalytic hydrogen has been observed to occur in either the SRAT or SME (pure slurry case), and these vessels are also likely to be considerably more dilute in both noble metals and formate ion (the two essential components to catalytic hydrogen generation) than the two primary process vessels. Rhodium certainly, and ruthenium likely, are present as metal-ligand complexes that are favored under certain concentrations of the surrounding species. Therefore, in the SMECT or RCT, where a small volume of SRAT or SME material would be significantly diluted, conditions would be less optimal for forming or sustaining the catalytic ligand species. Such conditions are likely to adversely impact the ability of the transferred mass to produce hydrogen at the same rate (per unit mass SRAT or SME slurry) as in the SRAT or SME vessels.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Bachelor of Science-Engineering Technology Program and Fuel Cell Education Program Concentration
The Hydrogen and Fuel Cell Technology education project has addressed DOE goals by supplying readily available, objective, technical, and accurate information that is available to students, industry and the public. In addition, the program has supplied educated trainers and training opportunities for the next generation workforce needed for research, development, and demonstration activities in government, industry, and academia. The project has successfully developed courses and associated laboratories, taught the new courses and labs and integrated the HFCT option into the accredited engineering technology and mechanical engineering programs at the University of North Carolina at Charlotte (UNCC). The project has also established ongoing collaborations with the UNCC energy related centers of the Energy Production & Infrastructure Center (EPIC), the NC Motorsports and Automotive Research Center (NCMARC) and the Infrastructure, Design, Environment and Sustainability Center (IDEAS). The results of the project activities are presented as two major areas – (1) course and laboratory development, offerings and delivery, and (2) program recruitment, promotions and collaborations. Over the project period, the primary activity has been the development and offering of 11 HFCT courses and accompanying laboratories. This process has taken three years with the courses first being developed and then offered each year over the timeframe.
08 HYDROGEN↗
Annual Report: Turbines
The FY12 NETL-RUA Turbine Thermal Management effort supported the Department of Energy (DOE) Hydrogen Turbine Program through conduct of novel, fundamental, basic, and applied research in the areas of aerothermal heat transfer, coatings development, and secondary flow control. This research project utilized the extensive expertise and facilities readily available at NETL and the participating universities. The research approach includes explorative studies based on scaled models and prototype coupon tests conducted under realistic high-temperature, pressurized, turbine operating conditions. This research is expected to render measurable outcomes that will meet DOE advanced turbine development goals of a 3- to 5-point increase in power island efficiency and a 30 percent power increase above the hydrogen-fired combined cycle baseline. In addition, knowledge gained from this project will further advance the aerothermal cooling and TBC technologies in the general turbine community. This project has been structured to address Development and design of aerothermal and materials concepts in FY12-13. Design and manufacturing of these advanced concepts in FY13. Bench-scale/proof-of-concept testing of these concepts in FY13-14 and beyond. The Turbine Thermal Management project consists of four tasks that focus on a critical technology development in the areas of aerothermal and heat transfer, coatings and materials development, design integration and testing, and a secondary flow rotating rig.
20 FOSSIL-FUELED POWER PLANTS↗