Hydrogen and Fuel Cells Program at Sandia National Laboratories.
Abstract not provided.
San Marchi, Christopher W.↗
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Sandia National Laboratories? Hydrogen and Fuel Cell Program Example Project Impacts.
Abstract not provided.
Zimmerman, Jonathan↗
Hydrogen Safety Knowledge Tools
With hydrogen gaining acceptance as an energy carrier for fuel cell vehicles and stationary fuel cell applications, a new community of hydrogen users is emerging and continues to grow. With this growth has come the need to spread the word about safe practices for handling, storing, and using hydrogen. Like all energy forms, hydrogen can be used safely through proper procedures and engineering techniques. However, hydrogen involves a degree of risk that must be respected, and the importance of avoiding complacency or haste in the safe conduct and performance of projects involving hydrogen cannot be overstated. To encourage and promote the safe use of hydrogen, Pacific Northwest National Laboratory (PNNL) has developed and continues to enhance two software tools in support of the U.S. Department of Energy's Fuel Cell Technologies Program: the Hydrogen Safety Best Practices online manual (www.H2BestPractices.org) and the Hydrogen Incident Reporting and Lessons Learned database (www.H2Incidents.org).
08 HYDROGEN↗
Semiannual VOC, Hydrogen, and Methane Data Summary Report for Reporting Period July 1, 2010 through December 31, 2010
This report was prepared by the U.S. Department of Energy (DOE) Carlsbad Field Office and Washington TRU Solutions LLC (the Permittees) in accordance with Sections 4.6.2.2 and 4.6.5.2 of the Waste Isolation Pilot Plant (WIPP) Hazardous Waste Facility Permit Number NM4890139088-TSDF (the Permit). This report documents the Volatile Organic Compound (VOC) Monitoring Program and Hydrogen and Methane Monitoring Program results for the 6-month period of July 1, 2010 through December 31, 2010.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Semi-Annual Voc, Hydrogen, and Methane Data Summary Report for Reporting Period July 1, 2011 through December 31, 2011
This report is submitted by the U.S. Department of Energy (DOE) Carlsbad Field Office and Washington TRU Solutions LLC (the Permittees) in accordance with Permit Part 4, Permit conditions 4.6.2.2 and 4.6.5.2 of the Waste Isolation Pilot Plant (WIPP) Hazardous Waste Facility Permit NM4890139088-TSDF (Permit). This report documents the Volatile Organic Compound (VOC) Monitoring Program and Hydrogen and Methane Monitoring Program results for the 6-month period of July 1, 2011 through December 31, 2011.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Semiannual VOC, Hydrogen, and Methane Data Summary Report for Report for Reporting Period January 1, 2011 through June 30, 2011
This report is submitted by the U.S. Department of Energy (DOE) Carlsbad Field Office and Washington TRU Solutions LLC (the Permittees) in accordance with Permit Part 4, Permit Conditions 4.6.2.2 and 4.6.5.2 of the Waste Isolation Pilot Plant (WIPP) Hazardous Waste Facility, Permit Number NM4890139088-TSDF (Permit). This report documents the Volatile Organic Compound (VOC) Monitoring Program and Hydrogen and Methane Monitoring Program results for the 6-month period of January 1, 2011 through June 30, 2011.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
H 2 Educate. Hydrogen and Fuel Cell Education Program
The H 2 Educate Program was a multi-year effort to educate middle school and high school students about hydrogen and fuel cell technologies. The National Energy Education Development (NEED) Project and the U.S. Department of Energy, along with non-financial partners embedded hydrogen and fuel cell curriculum in schools across the United States via teacher training workshops, conferences, and the design and delivery of curriculum and hands-on H 2 Educate Kits for classrooms.
08 HYDROGEN↗
Hydrogen wide area monitoring of LH2 releases
The characterization of liquid hydrogen (LH2) releases has been identified as an international research priority to expand the safe use of hydrogen as an energy carrier. The elucidation of LH2 release behavior will require the development of dispersion and other models, guided and validated by empirical field measurements such as those afforded by Hydrogen Wide Area Monitoring (HyWAM). HyWAM can be defined as the quantitative spatial and temporal three-dimensional monitoring of planned or unintentional hydrogen releases. With support provided through the FCH JU Prenormative Research for the Safe Use of Liquid Hydrogen (PRESLHY) program, HSE performed a series of LH2 releases to characterize the dispersion and pooling behavior of cold hydrogen releases. The NREL Sensor Laboratory developed a HyWAM system based upon a distributed array of point sensors that is amenable for profiling cold hydrogen plumes. The NREL Sensor Laboratory and HSE formally committed to collaborate on profiling the LH2 releases. This collaboration included the integration of the NREL HyWAM into the HSE LH2 release hardware. This was achieved through a deployment plan jointly developed by the NREL and HSE personnel. Under this plan, the NREL Sensor Laboratory provided multiple HyWAM modules that accommodated 32 sampling points for near-field hydrogen profiling during the HSE PRESLHY LH2 releases. The NREL HyWAM would be utilized throughout the LH2 release study performed under PRESLHY by HSE, including Work Package 3 (WP3—Release and Mixing--Rainout) and subsequent work packages (WP4—Ignition and WP5—Combustion). Under the auspices of the PRESLHY WP6 (Implementation), data and findings from the HSE LH2 Releases are to be made available to stakeholders in the hydrogen community. Comprehensive data analysis and dissemination is ongoing, but the integration of the NREL HyWAM into the HSE LH2 Release Apparatus and its performance as well as some key outcomes of the LH2 releases in WP3 are presented.
08 HYDROGEN↗
Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage
This program was dedicated to understanding the effect of impurities on Long-Term Thermal Cycling and aging properties of Complex Hydrides for Hydrogen Storage. At the start of the program we found reversibility between Li2NH+LiH LiH+LiNH2 (yielding ~5.8 wt.%H capacity). Then we tested the effect of impurity in H2 gas by pressure cycling at 255°C; first with industrial gas containing ppm levels of O2 and H2O as major impurities. Both these impurities had a significant impact on the reversibility and decreased the capacity by 2.65 wt.%H. Further increase in number of cycles from 500 to 1100 showed only a 0.2 wt%H more weight loss, showing some capacity is still maintained after a significant number of cycles. The loss of capacity is attributed to the formation of ~55 wt% LiH and ~30% Li2O, as major contaminant phases, along with the hydride Li2NH phase; suggesting loss of nitrogen during cycling. The effect of 100 ppm H2O in H2 also showed a decrease of ~2.5 wt.%H (after 560 cycles), and 100ppm O2 in H2; a loss of ~4.1 wt.%. Methane impurity (100 ppm, 100cycles), showed a very small capacity loss of 0.9 wt.%H under similar conditions. However, when Li3N was pressure cycled with 100ppmN2-H2 there were beneficial effects were observed (255oC); the reversible capacity increased to 8.4wt.%H after 853 cycles. Furthermore, with 20 mol.%N2-H2 capacity increased to ~10 wt.%H after 516 cycles. We attribute this enhancement to the reaction of nitrogen with liquid lithium during cycling as the Gibbs free energy of formation of Li3N (Go = -98.7 kJ/mol) is more negative than that of LiH (Go = -50.3 kJ/mol). We propose that the mitigation of hydrogen capacity losses is due to the destabilization of the LiH phase that tends to accumulate during cycling. Also more Li2NH phase was found in the cycled product. Mixed Alanates (3LiNH2:Li3AlH6) showed that 7 wt% hydrogen desorbed under dynamic vacuum. Equilibrium experiments (maximum 12 bar H2) showed up to 4wt% hydrogen reversibly stored in the material after the first desorption. The activation energy was found to be 51 kJ/mol, as compared to 81 kJ/mol for pure lithium alanate. It is proposed that based on the data obtained and CALPHAD modeling that the improvement in cycling is due to the formation of pure lithium (liquid at 255°C), which is able to react with nitrogen specifically forming Li3N. The presence of nitrogen in the 80/20 molar mixtures in a hydride bed along with hydrogen causes Li to form Li3N rather than LiH, and subsequently regenerates the Li2NH phase and yields a ~10 wt.%H reversibly.
08 HYDROGEN↗
Electronic Safety Resource Tools -- Supporting Hydrogen and Fuel Cell Commercialization
The Pacific Northwest National Laboratory (PNNL) Hydrogen Safety Program conducted a planning session in Los Angeles, CA on April 1, 2014 to consider what electronic safety tools would benefit the next phase of hydrogen and fuel cell commercialization. A diverse, 20-person team led by an experienced facilitator considered the question as it applied to the eight most relevant user groups. The results and subsequent evaluation activities revealed several possible resource tools that could greatly benefit users. The tool identified as having the greatest potential for impact is a hydrogen safety portal, which can be the central location for integrating and disseminating safety information (including most of the tools identified in this report). Such a tool can provide credible and reliable information from a trustworthy source. Other impactful tools identified include a codes and standards wizard to guide users through a series of questions relating to application and specific features of the requirements; a scenario-based virtual reality training for first responders; peer networking tools to bring users from focused groups together to discuss and collaborate on hydrogen safety issues; and a focused tool for training inspectors. Table ES.1 provides results of the planning session, including proposed new tools and changes to existing tools.
08 HYDROGEN↗
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↗
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.
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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↗
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↗