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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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NASA NTRS1986

Investigation of nickel hydrogen battery technology for the RADARSAT spacecraft

The low Earth orbit (LEO) operations of the RADARSAT spacecraft require high performance batteries to provide energy to the payload and platform during eclipse period. Nickel Hydrogen cells are currently competing with the more traditional Nickel Cadmium cells for high performance spacecraft applications at geostationary Earth orbit (GEO) and Leo. Nickel Hydrogen cells appear better suited for high power applications where high currents and high Depths of Discharge are required. Although a number of GEO missions have flown with Nickel Hydrogen batteries, it is not readily apparent that the LEO version of the Nickel Hydrogen cell is able to withstand the extended cycle lifetime (5 years) of the RADARSAT mission. The problems associated with Nickel Hydrogen cells are discussed in the contex of RADARSAT mission and a test program designed to characterize cell performance is presented.

Mccoy, D. A.↗
NASA NTRS1989

Fueling the National Aero-Space Plane with slush hydrogen

The National Aerospace Plane is a horizontal take off and landing, single stage-to-orbit vehicle using hydrogen as the fuel. The first flights are planned for the mid 1990s. The high heating value, cooling capacity, and combustion properties make hydrogen the fuel of choice, but the low density results in a large vehicle. Both the fuel cooling capacity and density are increased with the use of slush hydrogen and result in significant reductions in size of the vehicle. A national program to advance this technology and to find engineering solutions to the many design issues is now underway.

Hannum, Ned P.↗
NASA NTRS1989

Space Station Technology Summary

The completion of the Space Station Propulsion Advanced Technology Programs established an in-depth data base for the baseline gaseous oxygen/gaseous hydrogen thruster, the waste gas resistojet, and the associated system operations. These efforts included testing of a full end-to-end system at National Aeronautics and Space Administration (NASA)-Marshall Space Flight Center (MSFC) in which oxygen and hydrogen were generated from water by electrolysis at 6.89 MPa (1,000 psia), stored and fired through the prototype thruster. Recent end-to-end system tests which generate the oxygen/hydrogen propellants by electrolysis of water at 20.67 MPa (3,000 psia) were completed on the Integrated Propulsion Test Article (IPTA) at NASA-Johnson Space Center (JSC). Resistojet testing has included 10,000 hours of life testing, plume characterization, and electromagnetic interference (EMI) testing. Extensive 25-lbf thruster testing was performed defining operating performance characteristics across the required mixture ratio and thrust level ranges. Life testing has accumulated 27 hours of operation on the prototype thruster. A total of seven injectors and five thrust chambers were fabricated to the same basic design. Five injectors and three thrust chambers designed to incorporate improved life, performance, and producibility characteristics are ready for testing. Five resistojets were fabricated and tested, with modifications made to improve producibility. The lessons learned in the area of producibility for both the O2/H2 thrusters and for the resistojet have resolved critical fabrication issues. The test results indicate that all major technology issues for long life and reliability for space station application were resolved.

Iacabucci, R.↗
NASA NTRS1992

Application of computational fluid dynamics to the design of the Space Transportation Main Engine subscale nozzle

CFD analyses of the Space Transportation Main Engine film/dump cooled subscale nozzle are presented, with an emphasis on the timely impact of CFD in the design of the subscale nozzle secondary coolant system. Calculations were performed with the Generalized Aerodynamic Simulation Program (GASP), using a Baldwin-Lomas Turbulence model, and finite rate hydrogen-oxygen chemistry. Design iterations for both the secondary coolant cavity passage and the secondary coolant lip are presented. In addition, validation of the GASP chemistry and turbulence models by comparison with data and other CFD codes are presented for a hypersonic laminar separation corner, a backward facing step, and a 2D scramjet nozzle with hydrogen-oxygen kinetics.

Garrett, J. L.↗
NASA NTRS1999

Experimental Studies of the Heat Transfer to RBCC Rocket Nozzles for CFD Application to Design Methodologies

Rocket thrusters for Rocket Based Combined Cycle (RBCC) engines typically operate with hydrogen/oxygen propellants in a very compact space. Packaging considerations lead to designs with either axisymmetric or two-dimensional throat sections. Nozzles tend to be either two- or three-dimensional. Heat transfer characteristics, particularly in the throat, where the peak heat flux occurs, are not well understood. Heat transfer predictions for these small thrusters have been made with one-dimensional analysis such as the Bartz equation or scaling of test data from much larger thrusters. The current work addresses this issue with an experimental program that examines the heat transfer characteristics of a gaseous oxygen (GO2)/gaseous hydrogen (GH2) two-dimensional compact rocket thruster. The experiments involved measuring the axial wall temperature profile in the nozzle region of a water-cooled gaseous oxygen/gaseous hydrogen rocket thruster at a pressure of 3.45 MPa. The wall temperature measurements in the thruster nozzle in concert with Bartz's correlation are utilized in a one-dimensional model to obtain axial profiles of nozzle wall heat flux.

Santoro, Robert J.↗
NASA NTRS1999

Strutjet RBCC Engine Performance

In the past two years Strutjet Rocket Based Combined Cycle (RBCC) engine has been tested extensively under the Advanced Reusable Technology (ART) contract from NASA MSFC. RBCC Engines combine the high thrust to weight of the rocket with the high efficiency of the ramjet engine. This propulsion system has the potential to reduce the cost of launching payloads to orbit by up to a factor of 100. In the ART program we have conducted over 100 hot fire tests. The propellants have been hydrogen and oxygen. The Modes tested have included the Air Augmented Rocket (AAR) from M = 0 to 2.4, the Ramjet at M = 2.4 & 6, Scramjet at M = 6 & 8, Scram/Rocket at Mach 8 and Ascent Rocket in Vacuum. This invited paper will present an overview of these test results and plans for future development of this propulsion cycle.

Bulman, Mel↗
NASA NTRS2003

X-43C Plans and Status

X-43C Project is a hypersonic flight demonstration being executed as a collaboration between the National Aeronautics and Space Administration (NASA) and the United States Air Force (USAF). X-43C will expand the hypersonic flight envelope for air breathing engines beyond the history making efforts of the Hyper-X Program (X-43A). X-43C will demonstrate sustained accelerating flight during three flight tests of expendable X-43C Demonstrator Vehicles (DVs). The approximately 16-foot long X-43C DV will be boosted to the starting test conditions, separate from the booster, and accelerate from Mach 5 to Mach 7 under its own power and autonomous control. The DVs are to be powered by a liquid hydrocarbon-fueled, fuel-cooled, dual-mode, airframe integrated scramjet engine system developed under the USAF HyTech Program. The Project is managed by NASA Langley Research Center as part of NASA s Next Generation Launch Technology Program. Flight tests will be conducted by NASA Dryden Flight Research Center over water off the coast of California in the Pacific Test Range. The NASA/USAF/industry project is a natural extension of the Hyper-X Program (X-43A), which will demonstrate short duration (~ 10 seconds) gaseous hydrogen-fueled scramjet powered flight at Mach 7 and Mach 10 using a heavyweight, largely heat sink construction, experimental engine. The X-43C Project will demonstrate sustained accelerating flight from Mach 5 to Mach 7 (~ 4 minutes) using a flight-weight, fuel-cooled, scramjet engine powered by much denser liquid hydrocarbon fuel. The X-43C DV design flows from integrating USAF HyTech developed engine technologies with a NASA Air Breathing Launch Vehicle accelerator-class configuration and Hyper-X heritage vehicle systems designs. This paper describes the X-43C Project and provides background for NASA s current hypersonic flight demonstration efforts.

Moses, Paul L.↗
NASA NTRS2005

The Fuel Cell Powered Club Car Carryall

The NASA Glenn Research Center initiated development of the Fuel Cell Powered Club Car Carryall as a way to reduce pollution in industrial settings, reduce fossil fuel consumption and reduce operating costs for transportation systems. The Club Car Carryall provides an inexpensive approach to advance the state of the art in electric vehicle technology in a practical application. The project transfers space technology to terrestrial use via non-traditional partners, and provides power system data valuable for future aeronautics and space applications. The work was done under the Hybrid Power Management (HPM) Program. The Carryall is a state of the art, dedicated, electric utility vehicle. Hydrogen powered proton exchange membrane (PEM) fuel cells are the primary power source. Ultracapacitors were used for energy storage as long life, maintenance free operation, and excellent low temperature performance is essential. Metal hydride hydrogen storage was used to store hydrogen in a safe and efficient low-pressure solid form. The report concludes that the Fuel Cell Powered Club Car Carryall can provide excellent performance, and that the implementation of fuel cells in conjunction with ultracapacitors in the power system can provide significant reliability and performance improvements.

Eichenberg, Dennis J.↗
NASA NTRS2011

Launch Vehicle Demonstrator Using Shuttle Assets

The Advanced Concepts Office at NASA's George C. Marshall Space Flight Center undertook a study to define candidate early heavy lift demonstration launch vehicle concepts derived from existing space shuttle assets. The objective was to determine the performance capabilities of these vehicles and characterize potential early demonstration test flights. Given the anticipated budgetary constraints that may affect America's civil space program, and a lapse in U.S. heavy launch capability with the retirement of the space shuttle, an early heavy lift launch vehicle demonstration flight would not only demonstrate capabilities that could be utilized for future space exploration missions, but also serve as a building block for the development of our nation s next heavy lift launch system. An early heavy lift demonstration could be utilized as a test platform, demonstrating capabilities of future space exploration systems such as the Multi Purpose Crew Vehicle. By using existing shuttle assets, including the RS-25D engine inventory, the shuttle equipment manufacturing and tooling base, and the segmented solid rocket booster industry, a demonstrator concept could expedite the design-to-flight schedule while retaining critical human skills and capital. In this study two types of vehicle designs are examined. The first utilizes a high margin/safety factor battleship structural design in order to minimize development time as well as monetary investment. Structural design optimization is performed on the second, as if an operational vehicle. Results indicate low earth orbit payload capability is more than sufficient to support various vehicle and vehicle systems test programs including Multi-Purpose Crew Vehicle articles. Furthermore, a shuttle-derived, hydrogen core vehicle configuration offers performance benefits when trading evolutionary paths to maximum capability.

Creech, Dennis M.↗
NASA NTRS2018

Cryogenic Selective Surfaces

There are many challenges involved in deep-space exploration, but several of these can be mitigated, or even solved, by the development of a coating that reflects most of the Sun’s energy, yet still provides far-infrared heat emission. Such a coating would allow non-heat-generating objects in space to reach cryogenic temperatures without using an active cooling system. This would benefit deep-space sensors that require low temperatures, such as the James Webb Telescope focal plane array. It would also allow the use of superconductors in deep space, which could lead to magnetic energy storage rings, lossless power delivery, or perhaps a large-volume magnetic shield against galactic cosmic radiation. However, perhaps the most significant enablement achieved from such a coating would be the long-term, deep space storage of cryogenic liquids, such as liquid oxygen (LOX). In our Phase I NIAC study, we realized that a combination of scattering particles and a silver backing could yield a highly effective, very broadband, reflector that could potentially reflect more than 99.9% of the Sun’s irradiant power. We developed a sophisticated model of this reflector and theoretically showed that cryogenic temperatures could be achieved in deep space at one astronomical unit (1 AU) from the Sun. We showed how this new reflector could minimize heat conduction into the cryogenic tanks by coating the tank support struts. We then modelled a strawman architecture for a mission to Mars, using a coated LOX tank, coated struts, and infrared shields, to show that with our new coating it would be possible to maintain liquid oxygen passively. As a result of this work a patent application was generated and a paper published in Optics Letters. Our Phase II NIAC study had two primary goals, to develop a rigid version of the cryogenic selective surface proposed in Phase I and to test its performance in a simulated deep space environment. During the first year of the project the work concentrated on developing rigid tiles of BaF2, leading to tiles as large as 4 inches in diameter that transmitted very little visible light. In addition, during the first year a simulated deep space environment was created using a vacuum chamber and cryocooler. Using this facility, we showed that our BaF2 tiles absorbed less than ¼% of 375 nm radiation, a significant milestone for the work. During the second year of the project, we continued to develop the BaF2 tiles and we put significant effort into the construction of a deep space environment where we could project simulated solar radiation onto a sample. In the spring of 2018, we conducted our first solar simulator test with BaF2 and saw about 3.6% absorption. This is better than the state-of-the-art, but disappointing since predictions were for much lower absorption. We, erroneously, attributed this absorption to water retention by the BaF2, and decided to change materials. We considered several oxides and settled on yttrium oxide (Y2O3) for further development, because it is broadband, lightweight, has high index, and is hydrophobic. In July 2018 we conducted our first test of a rigid tile of Y2O3 in the simulated deep space environment and saw significant absorption again. We then realized that the issue was not water, but mid-wave radiation passing through the tile and being absorbed by the temperature sensor and the varnish used to hold it in place. We wrapped the sensor in silver foil, re-ran the test, and saw much lower absorption; only 1.1%. We then re-ran the BaF2 tile and saw 1.4% absorption. These values are almost adequate to maintain LOX in deep space, but we suspect that there are still issues in our test apparatus; we suspect thermocouple wires may be absorbing radiation. Further, post-NIAC, testing will better determine the performance of our new solar reflector. In order to restrict the size of this report, we will only briefly describe topics that we have previously published, allowing us to devote more time to new material. So minimal material will be devoted to modeling the material and deep space cryogenic storage, while longer sections will cover our material development, simulated deep space testing, and new applications. The Launch Service Program (LSP) requested that we explore ways to use this new coating to maintain LOX in low Earth Orbit and that work is described. In addition, the Nuclear Thermal Propulsion (NTP) Program asked us to explore ways to reduce the heat load for liquid hydrogen, resulting in the development of a spray-on version of the coating that should significantly improve in-space multi-layer insulation performance.

Robert C. Youngquist,↗
DOE OSTI2011

Market Transformation

This Fuel Cell Technologies Program fact sheet outlines current status and challenges in the market transformation of hydrogen and fuel cell technologies.

market transformation fuel cells hydrogen↗
DOE OSTI2016

HTTR-GT/H2 test plant - design study on helium gas turbine for the heat utilization system connected to JAEA's HTTR - 18674

In JAEA (Japan Atomic Energy Agency), the program of verification of combined system with helium gas turbine power generation and hydrogen production using nuclear heat which becomes the first in the world, is proceeding. From 2014 to 2015 Japanese Fiscal Year, the design study of the heat utilization system which is arranged in cascade to the heat supply system to supply the hydrogen production system and helium gas turbine system which are installed in the secondary helium-cooling system of High Temperature Engineering Test Reactor (HTTR) was performed and measure technologies of the system have been verified. MHI participated in the design study work of main equipment of this system. This paper reports the result of the design study of a helium gas turbine among those results. Self-sustaining condition (a power generation output is attained) is required for the gas turbine system in three modes of operation such as a) gas turbine individual operation, b) gas turbine + hydrogen production system combined operation, and c) hydrogen production system load loss and gas turbine independent shift operation]. By adopting a multi-stage centrifugal type impeller as a gas turbine and a compressor as a result of design study, it confirmed that all the mode-of-operation self-sustaining can be attained, and can attain a maximum of approx. 1 MWe power generation output on condition of the turbine inlet temperature of 560 deg. C, the turbine flow of 9.8 kg/sec, the compressor inlet temperature of 30 deg. C, and the compression ratio 1.3. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2024

A Mid-Century Net-Zero Scenario for the State of Wyoming and its Economic Impacts

Clean hydrogen has the potential to help achieve 10% economy-wide emissions reductions by 2050 relative to 2005, promote energy security and resilience, and develop a new economy in the United States. In 2030, the hydrogen economy could create about 100,000 new jobs to build new capital projects and clean hydrogen infrastructure. The Wyoming Energy Authority recently announced the state’s energy strategy, which establishes a goal of net-zero emissions by 2050. Under all likely scenarios, achieving a mid-century net-zero target will pose challenges and create opportunities for Wyoming’s energy sector. If executed properly, the transition could favorably affect the state’s economy overall in the long term. This research program examines the economic impact of fossil energy production in Wyoming and provides various predictions for future energy mixes to achieve net-zero emissions. Preliminary work suggests that Wyoming-based hydrogen production could have significant economic benefits and job creation implications for Wyoming. This study further assesses Wyoming’s opportunities to create hydrogen-based industries, assess economic impacts, identify knowledge gaps and research needs, and create a Hydrogen Center of Excellence to accelerate commercialization and deployment. This project helped to understand Wyoming's areas of focus for research and development and identified its areas of strength and potential challenges in creating a hydrogen ecosystem. As a result of this study, we estimate that for blue hydrogen produced from coal and gas resources, the overall cost reduction will be driven mainly by the carbon-sequestration tax credit and the improvement in carbon capture. Mature technologies, like SMR and PSA, will make limited contributions. They have no or limited reductions from an additional capacity deployment in future costs. We also understand the importance of continued support from public and private sectors for Carbon Capture and Storage (CCS)-related research, development, and demonstration programs at federal and state levels. The successful and efficient production of blue hydrogen requires a unique blend of energy resources, geology, regulation, law, and infrastructure. Wyoming has the distinction of meeting all these demands. The team also estimates that the availability and command of water resources accessible for hydrogen production are crucial for developing new projects. Water treatment, use, and disposal after treatment will also make projects possible. Primarily, this is relevant for hydrogen made using renewable energy. Wyoming has one of the best wind resource capacity in the nation. Harnessing this resource is challenging due to limited transmission line availability. Hydrogen could become one of the solutions to the stranded resource problem, primarily if the water availability challenge is addressed. Using produced oil & gas water could help to solve the problem. A commonly cited barrier to the expansion of hydrogen markets is the cost associated with constructing new pipelines, which typically require large amounts of capital to develop. Wyoming already possesses much of the export infrastructure needed to connect Wyoming’s hydrogen production with major markets across the West Coast, Pacific Northwest, Midwest, and Front Range regions of the United States, where a large portion of Wyoming’s natural gas is already transported. In addition to transportation by pipeline, rail transportation of hydrogen has also proven feasible. Wyoming uses its extensive railway system to transport large amounts of coal to its export partners across the United States. By using cryogenic or compressed-gas cars, Wyoming has the potential to add hydrogen to its existing network of railroad energy exports. The same technology may also be applied to hydrogen transport via trucks traveling interstate highways. Wyoming’s workforce is ready to meet the demands of clean hydrogen development. Many of the skills and training needed for hydrogen production are the same skills already possessed by Wyoming’s oil & gas and coal workforce. Many government and industry leaders expect clean hydrogen and other low-carbon energy projects to generate significant job growth and to recruit many already-trained oil & gas and coal workers whose jobs may be displaced. As energy companies seek to penetrate the markets for Wyoming hydrogen production, there is a natural mutual benefit to Wyoming’s workers and companies seeking to launch projects with the assistance of a trained workforce. Wyoming’s university and community college system have adopted several programs to ensure that highly qualified engineers and other technically skilled employees continue to graduate with skills to support the development of hydrogen and other innovative energy projects moving forward. Throughout the project, stakeholder outreach and education took many forms, including meetings with several major companies in the industry, collaborating with local government organizations, educational organizations, and national laboratories, tribal outreach and engagement, the sponsoring of several hydrogen-focused projects in many departments throughout the University of Wyoming, and developing a collaboration with international universities. The products of these collaborations consist of working relationships with several companies in the industry, educational institutions, national labs, and local government, as well as strong connections with individuals who will play an essential role in the success of the Hydrogen Energy Research Center.

08 HYDROGEN↗
NASA NTRS2022

XSP Methane Sensors Test and Evaluation Project “M-Step”

Methane sensor technology is employed in industry sectors from oil and gas to agriculture, landfills, and monitoring of natural emissions. The US oil and gas sector is extensive in scale, critical to fulfilling US energy needs, and deals with commodities presenting enormous challenges for personnel safety and the environment. Thus, it is imperative that they have accurate and responsive sensors to detect hazardous gases such as methane. US space launch systems will increasingly also use liquefied methane and liquefied natural gas (LNG), which is mostly methane, in quantities large and small, as main and auxiliary propulsion and power. Some of these systems will be reusable, which adds the unique challenge of processing a vehicle that has residual commodities and has returned to its launch site to be readied for its next launch. The methane sensors test and evaluation project (M-STEP) began within the context of a reusable launch system, the Defense Advanced Research Projects Agency (DARPA) Experimental Spaceplane (XSP) program, which would have employed a high-pressure gaseous methane and gaseous oxygen reaction control system. Although the XSP partnership between Boeing and DARPA was terminated by Boeing in early 2020, DARPA and KSC have continued to collaborate in the area of gas sensors with the hydrogen sensor test and evaluation project (H-STEP) and with M-STEP. The NASA Launch Services program (LSP) invested in M-STEP in FY 2021 “to evaluate and understand the state-of-the-art in methane gas sensors”. M-STEP and the LSP effort was complementary, pushing in the same direction to understand US launch system stakeholder needs and approaches, requirements internal (NASA) and external, and commercially available or forthcoming methane sensing technologies, practices, and approaches. In addition, M-STEP (as with H-STEP) enhances KSC capabilities and understanding of these technologies, informing agency investments and further research in these areas.

Tracy L. Gibson↗
DOE OSTI2010

Microchannel Reactor System for Catalytic Hydrogenation

We successfully demonstrated a novel process intensification concept enabled by the development of microchannel reactors, for energy efficient catalytic hydrogenation reactions at moderate temperature, and pressure, and low solvent levels. We designed, fabricated, evaluated, and optimized a laboratory-scale microchannel reactor system for hydrogenation of onitroanisole and a proprietary BMS molecule. In the second phase of the program, as a prelude to full-scale commercialization, we designed and developed a fully-automated skid-mounted multichannel microreactor pilot plant system for multiphase reactions. The system is capable of processing 1 – 10 kg/h of liquid substrate, and an industrially relevant immiscible liquid-liquid was successfully demonstrated on the system. Our microreactor-based pilot plant is one-of-akind. We anticipate that this process intensification concept, if successfully demonstrated, will provide a paradigm-changing basis for replacing existing energy inefficient, cost ineffective, environmentally detrimental slurry semi-batch reactor-based manufacturing practiced in the pharmaceutical and fine chemicals industries.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2015

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural with ALD overcoating (II) – Comparison between TiO2 and Al2O3 overcoatings

TiO2 atomic layer deposition (ALD) overcoatings were applied to copper chromite catalysts to increase the stability for 2-furfuraldehyde (“furfural”) hydrogenation. After overcoating, about 75% activity was preserved compared to neat copper chromite: much higher activity than an alumina ALD overcoated catalyst with a similar number of ALD cycles. The effects of ALD TiO2 on the active Cu nanoparticles were studied extensively using both in-situ TPR/isothermal-oxidation and in-situ furfural hydrogenation via Cu XAFS. The redox properties of Cu were modified only slightly by the TiO2 ALD overcoat. However, a subtle electronic interaction was observed between the TiO2 ALD layers and the Cu nanoparticles. With calcination at 500 °C the interaction between the TiO2 overcoat and the underlying catalyst is strong enough to inhibit migration and site blocking by chromite, but is sufficiently weaker than the interaction between the Al2O3 overcoat and copper chromite that it does not strongly inhibit the catalytic activity of the copper nanoparticles.

Zhang, Hongbo↗
NASA NTRS2015

Numerical Modeling of the Transient Chilldown Process of a Cryogenic Propellant Transfer Line

Before cryogenic fuel depots can be fully realized, efficient methods with which to chill down the spacecraft transfer line and receiver tank are required. This paper presents numerical modeling of the chilldown of a liquid hydrogen tank-to-tank propellant transfer line using the Generalized Fluid System Simulation Program (GFSSP). To compare with data from recently concluded turbulent LH2 chill down experiments, seven different cases were run across a range of inlet liquid temperatures and mass flow rates. Both trickle and pulse chill down methods were simulated. The GFSSP model qualitatively matches external skin mounted temperature readings, but large differences are shown between measured and predicted internal stream temperatures. Discrepancies are attributed to the simplified model correlation used to compute two-phase flow boiling heat transfer. Flow visualization from testing shows that the initial bottoming out of skin mounted sensors corresponds to annular flow, but that considerable time is required for the stream sensor to achieve steady state as the system moves through annular, churn, and bubbly flow. The GFSSP model does adequately well in tracking trends in the data but further work is needed to refine the two-phase flow modeling to better match observed test data.

Chilldown↗
DOE OSTI2018

One-pot catalytic conversion of biomass and alkanes: Kinetically coupling deoxygenation and dehydrogenation pathways

The stoichiometric hydrogen deficiency of carbohydrate feedstock implies that all conversion processes must remove oxygen and concurrently increase hydrogen content to form liquid hydrocarbon products. With support from the DOE Early Career program (DE-SC0008418) we have investigated the use of transition metal carbides for hydrodeoxygenation (HDO) chemistries using CH 4 and H 2 as co-reactants. We report that concurrently processing CH 4 and C 1 -C 3 oxygenates (oxygenate/CH 4 = 0.01-0.1) at 950 K on molybdenum carbide clusters encapsulated in zeolite micropores results in a staged bed with upstream CH 4 reforming and downstream CH 4 dehydroaromatization. Forward rates of CH 4 pyrolysis limited by CH 4 activation are unperturbed by the introduction of oxygenates with a (C/H) eff <0.25 after rigorously accounting for the thermodynamic reversibility caused by the H 2 produced in oxygenate reforming reactions and the fraction of the active catalyst bed deemed unavailable for CH 4 dehydroaromatization. A binomial distribution of 12 C/ 13 C isotopologues of CO is observed upon introduction of CH 3 13 COOH/CH 4 reactants suggesting that the introduction of oxygenates with a (C/H) eff <0.25 results in complete fragmentation of the oxygenate at these temperatures which in turn results in the invariance of forward rates of CH 4 pyrolysis when using CO 2 , HCOOH, or CH 3 COOH co-feeds. The stoichiometric loss of oxygen as CO when co-processing C 1 -C 3 oxygenates and CH 4 at these temperatures demonstrates that (C/H) eff =(C-O)/H is a single valued descriptor for oxygen removal on Mo/HZSM-5 catalysts. Separately, we have demonstrated the utility of transition metal carbides for vapor phase catalytic hydrodeoxygenation using molecular hydrogen with high selectivity for C-O cleavage and near absence of sequential hydrogenation reactions at atmospheric hydrogen pressure and illustrated that the faculty of transition metal carbides for selective hydrodeoxygenation arises due to oxygen-modification of the catalyst in situ. The oxophilic characteristics of these materials engender both the observed acid-metal catalytic bifunctionality and selectivity for hydrodeoxygenation. The evolution of catalyst surface composition and catalytic function under oxidative reaction environments proffers unique challenges in structural characterization of these materials and in this context, we developed and demonstrated the use of chemical titration and chemical transient studies to assess catalytic site identity and densities.

09 BIOMASS FUELS↗