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At least 127 records · Page 7

Final Report – Cooperative Research and Development Agreement between National Energy Technology Laboratory and Praxair, Inc.

Praxair and DOE-NETL entered into a collaborative research and development agreement (CRADA) in March 2019 to evaluate economic viability of chemical looping processes for hydrogen, CO, and syngas production in comparison to state-of-the-art conventional processes. Praxair had developed process configurations for producing hydrogen and CO using chemical looping processes. NETL had modeling and system design experience for the chemical looping reactor system. The goal for NETL is to provide performance and design information regarding the chemical looping portion of a potential commercial plant. Praxair’s goal is to evaluate chemical looping processes and try to identify a process that can be commercially relevant within a few years. A key to success for the program will be to develop a chemical looping reactor system that enables significant capital cost reduction and performance improvement for the overall process. This report describes chemical looping-based CO production process, chemical looping reactor system and oxygen carrier material as well as summary of technoeconomic analysis results. Also included in the report are a list of assumptions that were used for designing the chemical looping plant and a list of areas for further study required to validate some of these assumptions in future efforts. The initial goal was to design two chemical looping plants. Case 1 would produce 1 MM scfd Hydrogen from NG, and Case 2 would co-produce hydrogen and 5 MM scfd CO from NG. However, later in the collaboration, it was decided to drop Case 1 as Case 2 process already included hydrogen production.

Bayham, Samuel↗

HyPerPy (Hydrogen Extraction and Parabolic Trough Plant Performance Models using Python) [SWR-21-53]

The HyPerPy package consists of three scripts: 1) Model for Hydrogen Tracking in Parabolic Trough Power Plants, 2) Model for Receiver Performance, and 3) Model for Hydrogen Extraction Process. The power plant model (1) tracks hydrogen generation and transport within the circulating heat transfer fluid (HTF) of the power plant. This script is a transient, initial value simulation, in which the hydrogen concentration in the circulating HTF is 0 moles per cubic meter everywhere at time 0 seconds. Hydrogen concentration is calculated at discrete locations within the circulating HTF with 4-second time resolution. During each time step, the change in hydrogen concentration due to hydrogen generation and permeation is calculated for each location according to the local HTF temperature, vessel or piping properties, hydrogen concentration and partial pressure. This model predicts hourly hydrogen concentrations for typical operating days in the spring, summer, fall, and winter seasons. Data is used to create hourly mappings of hydrogen concentrations for a typical operating year. The receiver model (2) uses a 1-hour time step to estimate getter loading and annulus pressure. For each time step, the model uses HTF and ambient temperature data to estimate absorber tube, bellows, and getter temperatures for the time step. In addition, the model uses hourly HTF hydrogen concentrations that are generated by the power plant model (1), and annulus hydrogen pressure from the previous time step. With these data, the model calculates the moles of hydrogen permeating across the absorber tube and bellows during the time step. The net change in moles hydrogen is added or subtracted from the getter loading for the previous time step, and the hydrogen pressure is re-calculated based on getter loading and temperature. The model uses this algorithm to simulate hydrogen permeation and loading 24 hours per day, 365 days per year using seasonal temperature data. The model repeats these calculations for 25 years to create a mapping of receiver getter loading and annulus hydrogen pressure for four seasons of each year. The model for hydrogen extraction (3) estimates hydrogen extraction rates for a specific separation module configuration. The rate depends primarily on membrane area, vacuum pump performance, headspace gas flowrate to the membrane, and headspace gas hydrogen partial pressure. This model has two versions. The steady-state version predicts hydrogen extraction rates when the module is operating in separation mode. The dynamic version predicts hydrogen transfer through the membrane when the module is operating in sensor mode. The steady-state version is used with the plant model (1) to predict hydrogen partial pressures in the power plant when the extraction process is operating.

Glatzmaier, Gregory↗

Tin removal by an annular surface wave plasma antenna in an extreme ultraviolet lithography source

Tin contamination of the collector mirror surface remains one of the crucial issues of EUV (Extreme Ultraviolet) sources, directly impacting the availability of the tool. Hydrogen plasma-based tin removal processes employ hydrogen radicals and ions to interact with tin deposits to form gaseous tin hydride (SnH 4 ), which can be removed through pumping. An annular surface wave plasma (SWP) source developed at the University of Illinois—Urbana Champaign is integrated into the cone and perimeter of the collection mirror for in situ tin removal. The SWP is characterized by high ion and radical densities, low electron temperature, and local generation where etching is needed. This method has the potential to significantly reduce downtime and increase mirror lifetime. Radical probe measurements show hydrogen radical densities in the order of 10 19 m -3 , while Langmuir probe measurements show electron temperatures of up to 6 eV and plasma densities on the order of 10 17–18 m -3 . The generated ions are essential to the tin cleaning and have sufficiently low energy to cause no damage to the collector capping layer. Tin etch rates of up to 270 nm/min were observed in a variety of experimental conditions, including various powers, pressures, flowrates, and temperatures. In conclusion, the high etch rates demonstrated in this study exceed the expected contamination rate of the EUV source.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Automation of FARM from Alpha Phase to Beta Phase

Integrated energy systems (IES) combine different energy technologies in synergistic ways to achieve a more secure and economical energy supply. The RAVEN-based HYBRID framework and the RAVEN plugin for grid and capacity optimization (HERON) are used to find the optimal installed capacity and the optimal economical dispatch of each component of the IES, by respecting the limits on the production variables and the corresponding rates of variation (explicit constraints). Besides, there are other process variables whose evolution needs to be bounded to avoid damaging the components (e.g., condensers, heat exchangers, steam generators, etc.) or degrading the process efficiency (e.g., electrolysis in the hydrogen production process). To avoid violating these latter limits (implicit constraints), a proof-of-concept HERON validator based on Feasible Actuator Range Modifier (FARM-Alpha) was developed by Argonne National Laboratory in January 2021. This FARM-Alpha validator calculates the evolution of process variables on whom the implicit constraints are placed, and then provides feedback to HERON dispatcher to adjust the power setpoints of three IES components, i.e., Balance of Plant, Secondary Energy Source, and Thermal Energy Storage, so as to meet both the explicit and implicit constraints. FARM-Alpha was designed to assess the performance of FARM as a HERON validator only, i.e., the list of components and implicit operational constraints were hard-coded within the source code. The lack of flexibility of the corresponding software structure does not allow the deployment in production environment. This report describes the development and the implementation of an enhanced version of the FARM-based validator (FARM-Beta), which ensures more flexibility for the end user in modeling multiple IES configurations and scenarios. Several test cases of the power dispatch problem were then selected to demonstrate the capabilities offered by FARM-beta. The test cases illustrate the efficiency of the closed-loop optimization scheme and the capability to calculate set-point trajectories satisfying both explicit and implicit constraints.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Abstract for Umbrella CRADA between NETL and Susteon, Inc. (AGMT-0983)

NETL and Susteon will develop new technologies involving catalysts, sorbents, and membrane materials. These materials will be incorporated into chemical processes, scaled up, and evaluated for commercialization potential. Areas of interest include technologies for shale and natural gas processing and utilization; hydrogen production and processing; coal and syngas processing; and CO 2 capture and utilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Environmental considerations

A comparison was made between the environmental impact of the present nuclear-heated process and the currently commercial hydrogen-producing process utilizing coal for heating, i.e., the Lurgi coal gasification process. This comparison is based on the assumption that both plants produce the same quantity of H2, i.e., 269 cu m/sec of approximately the same purity, that all pollution abatement equipment is of the same design and efficiency for both the Lurgi process and the nuclear process, and that the energy required for the fresh nuclear fuel and the fuel recycle is generated in a power plant which is also provided with pollution abatement equipment. The pollution caused by the auxiliary units is also taken into account. As regards process water usage, the data show that the water required for the nuclear route, including the nuclear fuel production, is approximately 78% of that required for the Lurgi route.

Source record↗

High-performance SO 2 -depolarized electrolysis cell using advanced polymer electrolyte membranes

Three different proton conducting polymeric membrane materials (Nafion® 115, Nafion® 212, and sulfonated Diels-Alder polyphenylene [SDAPP]) were evaluated for use in SO 2 -depolarized electrolyzers for the production of hydrogen via the hybrid sulfur cycle. Their performance was measured using different water feed strategies to minimize overpotential losses while maintaining high product acid concentration. Both thin membranes (Nafion® 212 and SDAPP) showed performance superior to that of the thicker Nafion® 115. Here, the SDAPP membrane electrode assembly (MEA) performed well at higher acid concentrations, maintaining low ohmic and kinetic overpotentials. Finally, short-term (100-h) stability tests under constant current conditions showed minimal degradation for the SDAPP and Nafion® 212 MEAs. SDAPP MEA performance approached the targets needed to make the hybrid sulfur cycle a competitive process for hydrogen production (product acid concentration ≥65 wt% H 2 SO 4 at ≤ 0.6-V cell potential and ≥0.5 A-cm –2 current density).

08 HYDROGEN↗

The use of a very high temperature nuclear reactor in the manufacture of synthetic fuels

The three parts of a program directed toward creating a cost-effective nuclear hydrogen production system are described. The discussion covers the development of a very high temperature nuclear reactor (VHTR) as a nuclear heat and power source capable of producing the high temperature needed for hydrogen production and other processes; the development of a hydrogen generation process based on water decomposition, which can utilize the outputs of the VHTR and be integrated with many different ultimate hydrogen consuming processes; and the evaluation of the process applications of the nuclear hydrogen systems to assess the merits and potential payoffs. It is shown that the use of VHTR for the manufacture of synthetic fuels appears to have a very high probability of making a positive contribution to meeting the nation's energy needs in the future.

Farbman, G. H.↗

Energy management analysis of lunar oxygen production

Energy load models in the process of hydrogen reduction of ilmenite for lunar oxygen production are being developed. The load models will be used as a first step to ultimately determine the optimal energy system needed to supply the power requirements for the process. The goal is to determine the energy requirements in the process of hydrogen reduction of ilmenite to produce oxygen. The general approach is shown, and the objectives are to determine the energy loads of the processes in the system. Subsequent energy management studies will be made to minimize the system losses (irreversibilities) and to design optimal energy system power requirements. A number of processes are being proposed as possible candidates for lunar application and some detailed experimental efforts are being conducted within this project at the University of Arizona. Priorities are directed toward developing the energy models for each of the proposed processes being considered. The immediate goals are to identify the variables that would impact energy requirements and energy sources of supply.

Fazzolari, R.↗

Lunar Regolith Simulant Feed System for a Hydrogen Reduction Reactor System

One of the goals of In-Situ Resource Utilization (ISRU) on the moon is to produce oxygen from the lunar regolith which is present in the form of Ilmenite (FeTi03) and other compounds. A reliable and attainable method of extracting some of the oxygen from the lunar regolith is to use the hydrogen reduction process in a hot reactor to create water vapor which is then condensed and electrolyzed to obtain oxygen for use as a consumable. One challenge for a production system is to reliably acquire the regolith with an excavator hauler mobility platform and then introduce it into the reactor inlet tube which is raised from the surface and above the reactor itself. After the reaction, the hot regolith (-1000 C) must be expelled from the reactor for disposal by the excavator hauler mobility system. In addition, the reactor regolith inlet and outlet tubes must be sealed by valves during the reaction in order to allow collection of the water vapor by the chemical processing sub-system. These valves must be able to handle abrasive regolith passing through them as well as the heat conduction from the hot reactor. In 2008, NASA has designed and field tested a hydrogen reduction system called ROxygen in order to demonstrate the feasibility of extracting oxygen from lunar regolith. The field test was performed with volcanic ash known as Tephra on Mauna Kea volcano on the Big Island of Hawai'i. The tephra has similar properties to lunar regolith, so that it is regarded as a good simulant for the hydrogen reduction process. This paper will discuss the design, fabrication, operation, test results and lessons learned with the ROxygen regolith feed system as tested on Mauna Kea in November 2008.

Mueller, R. P.↗

Climate, air quality, and equity benefits from hydrogen substitution for fossil fuels used in process heat

Fossil fuel combustion for process heat in heavy industry accounts for ~15% of all United States CO 2 emissions and emits PM 2.5 and its precursors, emissions that have a disproportionate impact on minority populations. Decarbonizing process heat in the U.S. via hydrogen substitution presents an opportunity to reduce emissions of CO 2 and PM 2.5 and mitigate resulting exposure disparity. Here, we show that hydrogen substitution in steelmaking provides a large reduction in CO 2 emissions and air quality-related premature mortality, while hydrogen substitution in petroleum refining substantially benefits disadvantaged communities. When reductions in CO 2 emissions and premature mortality are monetized using standard regulatory values, we find that the sum of air pollution and climate benefits outweighs the difference in private cost associated with hydrogen substitution in steelmaking, regardless of the method of hydrogen production. The approach developed here can support evaluations of equity-focused decarbonization strategies in other industries and for specific sites.

08 HYDROGEN↗

The GA sulfur-iodine water-splitting process - A status report

The development of a sulfur-iodine thermal water splitting cycle is described. The process features a 50% thermal efficiency, plus all liquid and gas handling. Basic chemical investigations comprised the development of multitemperature and multistage sulfuric acid boost reactors, defining the phase behavior of the HI/I2/H2O/H3PO4 mixtures, and development of a decomposition process for hydrogen iodide in the liquid phase. Initial process engineering studies have led to a 47% efficiency, improvements of 2% projected, followed by coupling high-temperature solar concentrators to the splitting processes to reduce power requirements. Conceptual flowsheets developed from bench models are provided; materials investigations have concentrated on candidates which can withstand corrosive mixtures at temperatures up to 400 deg K, with Hastelloy C-276 exhibiting the best properties for containment and heat exchange to I2.

Besenbruch, G. E.↗

Selection process for trade study: Reusable Hydrogen Composite Tank System (RHCTS)

This document describes the selection process that will be used to identify the most suitable structural configuration option for an SSTO winged vehicle capable of delivering 25,000 lbs to a 220 nm circular orbit at 51.6 degree inclination. The most suitable RHCTS is within this configuration and will be the prototype design for subsequent design and analysis and the basis for the design and fabrication of a scale test article to be subjected to life cycle testing. The selection process for this TA 1 trade study is the same as that for the TA 2 trade study. As the trade study progresses additional insight may result in modifications to the selection criteria within in this process. Such modifications will result in an update of this document as appropriate.

Greenberg, H. S.↗

Kinetic and modeling studies of the mechanism of the dehydrogenation of Mg(BH 4 ) 2 to Mg(B 3 H 8 ) 2

Since its discovery over 15 years ago, the reversible dehydrogenation of Mg(BH 4 ) 2 to Mg(B 3 H 8 ) 2 has remained one of the more intriguing hydrogen-cycling systems. While the mechanism of this reaction has been the subject of a good deal of speculation and computational studies, prior to this work it had not been probed through kinetic studies. Previous reports of the dehydrogenation of Mg(BH 4 ) 2 to Mg(B 3 H 8 ) 2 have not included kinetic studies. The present studies have shown that the dehydrogenation of Mg(BH 4 ) 2 to Mg(B 3 H 8 ) 2 is suppressed by hydrogen pressure indicating that the rate-limiting step in this process involves hydrogen elimination. Computational modeling of kinetic data obtained from monitoring the hydrogen elimination from Mg(BH 4 ) 2 to Mg(B 3 H 8 ) 2 under static vacuum over a range of temperatures supports that the dehydrogenation occurs through a reversible three-step process in which the elimination of hydrogen from the [B 3 H 10 ] − intermediate is rate limiting. A mechanism involving the low energy transfer of neighboring BH3 groups is proposed to account for the formation of [B 3 H 8 ] − at relatively low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Biogeochemistry in Anaerobic and Photosynthetic Ecosystems

The simple biochemistry of molecular hydrogen is central to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. In anoxic sediments, a great majority of microbial redox processes involve hydrogen as a reactant, product or potential by-product. Accordingly, the energetics (thermodynamics) of each of these processes is affected by variations in local H2 concentrations. It has long been established that this effect is important in governing microbe-microbe interactions and there are multiple demonstrations that "interspecies hydrogen transfer" can alter the products of, inhibit/stimulate, or even reverse microbial metabolic reactions. In anoxic sediments, H2 concentrations themselves are thought to be controlled by the thermodynamics of the predominant H2-consuming microbial process. In sediments from Cape Lookout Bight, this relationship quantitatively describes the co-variation of H2 concentrations with temperature (for methanogens and sulfate reducers) and with sulfate concentration (for sulfate reducers). The quantitative aspect is import= for two reasons: 1) it permits the modeling of H2-sensitive biogeochemistry, such as anaerobic methane oxidation or pathways of organic matter remineralization, as a function of environmental controls; 2) for such a relationship to be observed requires that intracellular biochemistry and bioenergetics are being directly expressed in a component of the extracellular medium. H2 could therefore be utilized a non-invasive probe of cellular energetic function in intact microbial ecosystems. Based on the latter principle we have measured down-core profiles of H2 and other relevant physico-chemical parameters in order to calculate the metabolic energy yields (DG) that support microbial metabolism in Cape Lookout Bight sediments. Methanogens in this system apparently function with energy yields significantly smaller than the minimum requirements suggested by pure culture studies. Our recent work has extended the study of hydrogen to cyanobacterial mat communities. The large amounts of reducing power generated during photosynthetic activity carry the potential to contribute a swamping term to the H2 economy of the anaerobic microbial populations within the mat - and thereby to alter the population structure and biogeochemical function of the mat as a whole. In hypersaline microbial mats, we observe a distinct diel cycle in H2 production and a substantial corresponding flux. On an early Earth dominated by microbial mats, this transmission of photosynthetic reducing power may have carried important implications for both biospheric and atmospheric evolution.

Hoehler, Tori M.↗

Process Considerations for the Production of Hydrogen via Steam Reforming of Oxygenated Gases from Biomass Pyrolysis and Other Conversion Processes

Abstract In 2021, average CO 2 emissions was 9.7 g CO 2 /g H 2 produced, primarily based on steam methane reforming (SMR) technology that currently dominates hydrogen production. The substitution of natural gas (NG) and other fossil feedstocks in SMRs with renewable gases may be considered as an option for reducing greenhouse gas emissions. This analysis explores process impacts and constraints associated with the potential introduction of biogenic gases into SMRs. The results indicate that replacing NG in the fuel train of the SMR, followed by partial replacement of NG in the feed train may be a feasible approach. For the CO‐ and CO 2 ‐rich gas compositions assumed in this analysis the results indicate that feed train may accommodate up to 25 mole % of biogenic gases using allowances in existing designs and/or with small modifications, while maintaining similar hydrogen output. NG substitution in higher proportions require more major changes because of increased flow rates and heat exchange requirements in the system. Biogenic gases with lower CO 2 and higher calorific values are advantageous for NG substitution, and dry reforming using the CO 2 present in the feed gas can reduce steam consumption and increase process efficiency within limits where coking does not become a new constraint.

08 HYDROGEN↗

Catalytic Hydrogen Production from Methane: A Review on Recent Progress and Prospect

Natural gas (Methane) is currently the primary source of catalytic hydrogen production, accounting for three quarters of the annual global dedicated hydrogen production (about 70 M tons). Steam–methane reforming (SMR) is the currently used industrial process for hydrogen production. However, the SMR process suffers with insufficient catalytic activity, low long-term stability, and excessive energy input, mostly due to the handling of large amount of CO 2 coproduced. With the demand for anticipated hydrogen production to reach 122.5 M tons in 2024, novel and upgraded catalytic processes are desired for more effective utilization of precious natural resources. In this review, we summarized the major descriptors of catalyst and reaction engineering of the SMR process and compared the SMR process with its derivative technologies, such as dry reforming with CO 2 (DRM), partial oxidation with O 2 , autothermal reforming with H 2 O and O 2 . Finally, we discussed the new progresses of methane conversion: direct decomposition to hydrogen and solid carbon and selective oxidation in mild conditions to hydrogen containing liquid organics (i.e., methanol, formic acid, and acetic acid), which serve as alternative hydrogen carriers. We hope this review will help to achieve a whole picture of catalytic hydrogen production from methane.

08 HYDROGEN↗