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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Biological lignocellulose solubilization: Comparative evaluation of biocatalysts and enhancement via cotreatment

Feedstock recalcitrance is the most important barrier impeding cost-effective production of cellulosic biofuels. Pioneer commercial cellulosic ethanol facilities employ thermochemical pretreatment and addition of fungal cellulase, reflecting the main research emphasis in the field. However, it has been suggested that it may be possible to process cellulosic biomass without thermochemical pretreatment using thermophilic, cellulolytic bacteria. Thus, to further explore this idea, we examine the ability of various biocatalysts to solubilize autoclaved but otherwise unpretreated cellulosic biomass under controlled but not industrial conditions.

09 BIOMASS FUELS↗
DOE OSTI2016

IS Process Hydrogen Production Test for Components and System Made of Industrial Structural Material (II) - H{sub 2}SO{sub 4} decomposition, HI Distillation, and HI Decomposition Section - 18629

Japan Atomic Energy Agency (JAEA) has been conducting research and development on the thermochemical iodine sulfur (IS) process for nuclear-powered hydrogen production. The IS process is one of the promising candidates of heat application of High-Temperature Gas-Cooled Reactors. The IS process consists of three chemical reactions: Bunsen reaction, hydriodic acid (HI) decomposition and sulfuric acid (H{sub 2}SO{sub 4}) decomposition. It is necessary for component materials to have high corrosion resistance because high-temperature strong acids such as HI and H{sub 2}SO{sub 4} are used in the IS process. JAEA, so far, achieved to produce hydrogen for one week continuously with a hydrogen production rate of approximately 30 NL/h by a test apparatus made of glass and fluoro-resin material. As a next step toward practical application, we test-fabricated main components, that is, Bunsen reactor, sulfuric acid decomposer, and HI decomposer, made of industrial materials and investigated their integrity in the practical corrosive environments of the IS process. Based on their results, we have constructed a 100 NL/h-H{sub 2}-scale test apparatus made of industrial materials. This test apparatus is divided by chemical reaction and unit operation into five sections: Bunsen section, H{sub 2}SO{sub 4} decomposition section, HI concentration section, HI distillation section, and HI decomposition section. First, we investigated performance of components in each section. This report discusses test results of the H{sub 2}SO{sub 4} decomposition section, HI distillation section, and HI decomposition section. (authors)

08 HYDROGEN↗
DOE OSTI2026

Techno-Economic and Life Cycle Assessment of Chemical Recycling and Upcycling of Mixed Plastics Waste Containing Poly-vinyl-chloride

Developing technologies that completely remove chlorine from plastic waste can allow its chemical recycling and upcycling with catalytic methods. Here, this study compares eight processes involving different dechlorination methods (absorption columns, adsorption in beds of zeolites, catalytic dechlorination, and dissolution in ionic liquids) and chemical conversion technologies (incineration, pyrolysis, hydrogenolysis) to upgrade mixed plastics waste to various products (e.g., electricity, fuels, virgin polymers, and lubricant oil). The analysis determines that the absorption of chlorine in columns with basic aqueous solutions is limited to plastics waste with PVC concentrations below 0.1%. Dissolution in ionic liquids is not cost-competitive. On the contrary, two-step processes with catalytic dechlorination followed by thermochemical catalytic depolymerization, either pyrolysis or hydrogenolysis, significantly improve process economics and emissions. The most economically viable alternative is hydrogenolysis for producing lubricants, while the technology with the lowest global warming potential is chemical recycling via catalytic pyrolysis.

circular economy↗
DOE OSTI2022

A Thermogravimetric Temperature-Programmed Thermal Redox Protocol for Rapid Screening of Metal Oxides for Solar Thermochemical Hydrogen Production

As combinatorial and computational methods accelerate the identification of potentially suitable thermochemically-active oxides for use in solar thermochemical hydrogen production (STCH), the onus shifts to quickly evaluating predicted performance. Traditionally, this has required an experimental setup capable of directly carrying out a two-stage thermochemical water-splitting process. But this can be a difficult endeavor, as most off-the-shelf equipment cannot adequately deal simultaneously with the high temperatures, varying oxygen partial pressures, and high H 2 O partial pressures required; achieving sufficient temporal sensitivity to accurately quantify the kinetics is also a major challenge. However, as proposed here, a less complicated experiment can be used as a first screening for thermochemical water splitting potential. Temperature-Programmed Thermal Redox (TPTR) using thermogravimetry evaluates the thermal reduction behavior of materials. This technique does not require water splitting or CO 2 -splitting analogs but can nonetheless predict water-splitting performance. Three figures of merit are obtained from the TPTR experiment: reduction onset temperature, extent of reduction, and extent of recovery upon reoxidation. These metrics can collectively be used to determine if a material is capable of thermochemical water-splitting, and, to good approximation, predict whether the thermodynamics are favorable for use under more challenging high-conversion conditions. This paper discusses the pros and cons of using TPTR and proposes a protocol for use within the STCH community.

08 HYDROGEN↗
DOE OSTI2021

Getting Hydrogen to the Gigaton Scale

Due to its ability to perform clean, efficient processes, hydrogen has long been promoted as the energy carrier of the future, but recent activity and advances suggest a tipping point has been reached as hydrogen is now being recognized by much of the world for its unique capabilities to strongly support global efforts in achieving climate neutrality. The coming decades will require a massive increase in the amount of hydrogen used in the energy system as well as a transition from largely thermochemical to predominantly electrochemical processes involving hydrogen. For this to happen, hydrogen will need to globally approach the gigaton-scale on an annual basis. Thus, before hydrogen can fully achieve its potential, challenges that need to be addressed include achieving scale and further research and development (R&D) advances.

climate neutrality↗
DOE OSTI2018

A parametric study of ignition dynamics at ECN Spray A thermochemical conditions using 2D DNS

The ignition process in diesel engines is highly complex and incompletely understood. Here, two-dimensional direct numerical simulations are performed to investigate the ignition dynamics and their sensitivity to thermochemical and mixing parameters. The thermochemical and mixing conditions are matched to the benchmark Spray A experiment from the Engine Combustion Network. The results reveal a complex ignition process with overlapping stages of: low-temperature ignition (cool flames), rich premixed ignition, and nonpremixed ignition, which are qualitatively consistent with prior experimental and numerical investigations, however, this is the first time that fully-resolved simulations have been reported at the actual Spray A thermochemical condition. Parametric variations are then performed for the Damköhler number Da, oxidiser temperature, oxygen concentration, and peak mixture fraction (a measure of premixedness), to study their effect on the ignition dynamics. It is observed that with both increasing oxidiser temperature and decreasing oxygen concentration, that the cool flame moves to richer mixtures, the overlap in the ignition stages decreases, and the (nondimensional) time taken to reach a fully burning state increases. With increasing Da, the cool-flame speed is decreased due to lower mean mixing rates, which causes a delayed onset of high-temperature ignition. With increasing peak mixture fraction, the onset of each stage of ignition is not affected, but the overall duration of the ignition increases leading to a longer burn duration. In conclusion, the results suggest that turbulence–chemistry interactions play a significant role in determining the timing and location in composition space of the entire ignition process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

An Overview of Natural Gas Conversion Technologies for Co-Production of Hydrogen and Value-Added Solid Carbon Products

This report was prepared in response to the U.S. Department of Energy Fuel Cell Technologies Office Congressional Appropriation language to support research on carbon-free production of hydrogen using new chemical processes that utilize natural gas to produce solid carbon and hydrogen. The U.S. produces 9-10 million tons of hydrogen annually with more than 95% of the hydrogen produced by steam-methane reforming (SMR) of natural gas. SMR is attractive because of its high hydrogen yield; but it also converts the carbon to carbon dioxide. Non-oxidative thermal decomposition of methane to carbon and hydrogen is an alternative to SMR and produces CO 2 -free hydrogen. The produced carbon can be sold as a co-product, thus providing economic credit that reduces the delivered net cost of hydrogen. The combination of producing hydrogen with potentially valuable carbon byproducts has market value in that this allows greater flexibility to match the market prices of hydrogen and carbon. That is, the higher value product can subsidize the other in pricing decisions. In this report we highlight the relevant technologies reported in the literature—primarily thermochemical and plasma conversion processes—and recent research progress and commercial activities. Longstanding technical challenges include the high energetic requirements (e.g., high temperatures and/or electricity requirements) necessary for methane activation and, for some catalytic processes, the separation of solid carbon product from the spent catalyst. We assess current and new carbon product markets that could be served given technological advances, and we discuss technical barriers and potential areas of research to address these needs. We provide preliminary economic analysis for these processes and compare to other emerging (e.g., electrolysis) and conventional (e.g., SMR) processes for hydrogen production. The overarching conclusion of this study is that the cost of hydrogen can be potentially reduced to target levels of $2/kg with the co-production and sale of a sufficiently high-value carbon product. Technological advances are required to understand the reaction conditions and design reactor systems that can achieve high yields of the select carbon products and segregate or separate the high-value carbon products, and optimize the production process for both hydrogen and carbon.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2015

Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal catalysts, and consumes less hydrogen, if methanation can be mitigated. Our methanation data on Pt and Rh indicate effective suppression of methanation. Our data also show that our catalysts are less susceptible to coking; and unlike NiMo and CoMo, precious metal catalysts are not deactivated by water, a by-product of HDO of algae oil. Finally, our catalysts do not need to be sulfided to be active. A rigorous techno-economic analysis of our process for commercial scale production of 10,000 barrels per day of hydrotreated algae oil, with nutraceuticals co-product claiming only 0.05% of the raw algae oil, indicates an estimated plant gate price of ~$10/gal. Sensitivity analysis shows that critical parameters affecting sale price include (1) algae doubling time (2) biomass oil content (3) CAPEX, and (4) moisture content of post extracted algae residue. Modest improvements in these areas will result in enhanced and competitive economics. Based on a life cycle assessment for greenhouse gas emission, we found that if algae oil replaced 10% of the US consumption, this would result in a CO2e reduction of 210,000 tons per day. Improving the drying process for animal feed by 50% would result in further significant reduction in CO2e.

09 BIOMASS FUELS↗
DOE OSTI2018

Thermochemical wastewater valorization via enhanced microbial toxicity tolerance

Thermochemical (TC) biomass conversion processes such as pyrolysis and liquefaction generate considerable amounts of wastewater, which often contains highly toxic compounds that are incredibly challenging to convert via standard wastewater treatment approaches such as anaerobic digestion. These streams represent a cost for TC biorefineries, and a potential valorization opportunity, if effective conversion methods are developed. The primary challenge hindering microbial conversion of TC wastewater is toxicity. In this study, we employ a robust bacterium, Pseudomonas putida , with TC wastewater streams to demonstrate that aldehydes are the most inhibitory compounds in these streams. Proteomics, transcriptomics, and fluorescence-based immunoassays of P. putida grown in a representative wastewater stream indicate that stress results from protein damage, which we hypothesize is a primary toxicity mechanism. Constitutive overexpression of the chaperone genes, groEL, groES, and clpB, in a genome-reduced P. putida strain improves the tolerance towards multiple TC wastewater samples up to 200-fold. Moreover, the concentration ranges of TC wastewater are industrially relevant for further bioprocess development for all wastewater streams examined here, representing different TC process configurations. Furthermore, we demonstrate proof-of-concept polyhydroxyalkanoate production from the usable carbon in an exemplary TC wastewater stream. Altogether, this study demonstrates that protein quality control machinery and repair mechanisms can enable substantial gains in microbial tolerance to highly toxic substrates, including heterogeneous waste streams. When coupled to other metabolic engineering advances such as expanded substrate utilization and enhanced product accumulation, this study generally enables new strategies for biological conversion of highly-toxic, organic-rich wastewater via engineered aerobic monocultures or designer consortia.

09 BIOMASS FUELS↗
DOE OSTI2022

Accelerated Discovery of Solar Thermochemical Hydrogen Production Materials via High-Throughput Computational and Experimental Methods

In this project, combinatorial synthesis and testing methods were combined with high-throughput materials theory calculations to greatly accelerate the discovery of thermodynamically suitable candidates for green hydrogen production via a two-stage solar thermochemical water splitting (STCH) process. Over the course of the project, more than 8000 quinary and higher oxide compositions were computationally screened for STCH viability, and detailed stability calculations were performed for more than 30 of the most promising identified compositional archetypes. As a result, three new STCH capable compositional families were discovered and experimentally verified. The first, Ce x Sr 2-x MnO 4 (CSM), represents the first known Ruddlesden-Popper compound to show STCH activity, and thus demonstrates that perovskite-related structures may hold promise for this application. The second family, Sr 1-x Ce x MnO 3 (SCM), is the simple perovskite sister-analog to CSM. Sr 0.7 Ce 0.3 MnO 3 (SCM30), a member of this compositional family, was found to produce the highest hydrogen yields of any compound tested in this project, exceeding the end of project milestone target of > 150 μmol H 2 /gram oxide at a reduction temperature of 1350 °C, although only at steam-to-hydrogen ratios greater than 1000:1. Finally, we proved that a third novel Sr-and Mn-containing family, Sr 1-x Ca x Ti 1-y Mn y O 3 (SCTM), which was identified by Materials Project tools, also splits water. The behavior of the SCTM system was found to be similar to the previously discovered Sr 1-x La x Al 1-y Mn y O 3 (SLMA) family, albeit with lower H 2 yields. Across the three thrusts of the project (computational, combinatorial, and bulk testing), five journal articles were published. As part of Program End Analysis and Data Dissemination, relevant data used for the publications was uploaded to the HydroGEN Data Hub for public access, and in certain cases, results were added to public materials databases.

08 HYDROGEN↗
DOE OSTI2024

Aqueous-phase product treatment and monetization options of wet waste hydrothermal liquefaction: Comprehensive techno-economic and life-cycle GHG emission assessment unveiling research opportunities

While wet waste hydrothermal liquefaction technology has a high biofuel yield, a significant amount of the carbon and nitrogen in the feedstock reports to the aqueous-phase product. Pretreatment of this stream before sending to a conventional wastewater plant is essential or at the very least, advisable. In this work, techno-economic and life-cycle assessments were conducted for the state-of-technology baseline and four aqueous-phase product treatment and monetization options based on experimental data. Further, these options can cut minimum fuel selling prices by up to 13 % and life-cycle greenhouse gas emissions by up to 39 % compared to the baseline. These findings highlight the substantial influence of aqueous produce treatment strategies on the entire wet waste hydrothermal liquefaction process, demonstrating the potential for optimizing economic viability and environmental impact through further research and development of milder treatment methods and diversified by-product valorization pathways.

09 BIOMASS FUELS↗
DOE OSTI2014

Development of GREET Catalyst Module

Catalysts are critical inputs for many pathways that convert biomass into biofuels. Energy consumption and greenhouse gas (GHG) emissions during the production of catalysts and chemical inputs influence the life-cycle energy consumption, and GHG emissions of biofuels and need to be considered in biofuel life-cycle analysis (LCA). In this report, we develop energy and material flows for the production of three different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5]) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET™) catalyst module. They were selected because they are consumed in existing U.S. Department of Energy (DOE) analyses of biofuel processes. For example, a thermochemical ethanol production pathway (indirect gasification and mixed alcohol synthesis) developed by the National Renewable Energy Laboratory (NREL) uses olivine, DEPG, and tar reforming and alcohol synthesis catalysts (Dutta et al., 2011). ZSM-5 can be used in biofuel production pathways such as catalytic upgrading of sugars into hydrocarbons (Biddy and Jones, 2013). Other uses for these compounds and catalysts are certainly possible. In this report, we document the data sources and methodology we used to develop material and energy flows for the catalysts and compounds in the GREET catalyst module. In Section 2 we focus on compounds used in the model Dutta et al. (2011) developed. In Section 3, we report material and energy flows associated with ZSM-5 production. Finally, in Section 4, we report results.

09 BIOMASS FUELS↗
DOE OSTI2020

High temperature water electrolysis testing of gold-based electrodes for H 2 production

The Hybrid Sulfur (HyS) process is a promising thermochemical water-splitting cycle with global scale hydrogen production potential. The SO 2 -depolarized electrolyzer (SDE) is a critical component of the cycle. At the core of the SDE is the membrane-electrode assembly (MEA), which consists of a polymer electrolyte membrane (PEM) sandwiched between two electrocatalyst layers. New electrocatalyst and membrane materials are being developed with the goals of improving the electrolyzer performance and extending the lifetime of the MEA. In this work, we evaluated the performance of three different membranes and optimized operating conditions, resulting is one of the highest performances in the literature.

08 HYDROGEN↗
NASA NTRS1975

An analysis of hydrogen production via closed-cycle schemes

A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

Chao, R. E.↗
NASA NTRS1975

Hydrogen production

The state of hydrogen production technology is evaluated. Specific areas discussed include: hydrogen production fossil fuels; coal gasification processes; electrolysis of water; thermochemical production of hydrogen; production of hydrogen by solar energy; and biological production of hydrogen. Supply options are considered along with costs of hydrogen production.

England, C.↗
DOE OSTI2016

Hydrothermal Liquefaction of Wastewater Treatment Plant Solids

Feedstock cost is the greatest barrier to the commercial production of biofuels. The merits of any thermochemical or biological conversion process are constrained by their applicability to the lowest cost feedstocks. At PNNL, a recent resource assessment of wet waste feedstocks led to the identification of waste water treatment plant (WWTP) solids as a cost-negative source of biomass. WWTP solids disposal is a growing environmental concern [1, 2] and can account for up to half of WWTP operating costs. The high moisture content is well-suited for hydrothermal liquefaction (HTL), avoiding the costs and parasitic energy losses associated with drying the feedstock for incineration. The yield and quality of biocrude and upgraded biocrude from WWTP solids is comparable to that obtained from algae feedstocks but the feedstock cost is $500-1200 less per dry ton. A collaborative project was initiated and directed by the Water Environment & Reuse Foundation (WERF) and included feedstock identification, dewatering, shipping to PNNL, conversion to biocrude by HTL, and catalytic hydrothermal gasification of the aqueous byproduct. Additional testing at PNNL included biocrude upgrading by catalytic hydrotreatment, characterization of the hydrotreated product, and a preliminary techno-economic analysis (TEA) based on empirical results. This short article will cover HTL conversion and biocrude upgrading. The WERF project report with complete HTL results is now available through the WERF website [3]. The preliminary TEA is available as a PNNL report [4].

biocrude upgrading↗
DOE OSTI2018

Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy

We present that the plant cell wall biopolymers lignin, cellulose and hemicellulose are potential renewable sources of clean biofuels and high-value chemicals. However, the complex 3D structure of lignocellulosic biomass is recalcitrant to deconstruction. Major efforts to overcome this recalcitrance have involved pretreating biomass before catalytic processing. This Perspective describes recent work aimed at elucidating the molecular-level physical phenomena that drive biomass assembly. These are at play in commonly employed aqueous-based and thermochemical pretreatments. Lastly, several key processes have been found to be driven by biomass solvation thermodynamics, an understanding of which therefore facilitates the rational improvement of methods aimed at the complete solubilization and fractionation of the major biomass components.

09 BIOMASS FUELS↗
DOE OSTI2018

Solar Thermochemical Fuel Production via a Novel Low Pressure, Magnetically Stabilized, Non-volatile Iron Oxide Looping Process (University of Florida)

The UF Solar Fuels team has developed a modular reactor at the 10kW scale for the thermochemical conversion of H 2 O and CO 2 to H 2 and CO, respectively, using concentrated solar energy to drive high-temperature redox reactions. Various materials, including ferrites, doped and mixed metal ferrites, and ceria, were investigated and reported on. Ceria was chosen as the reactive material, with thermogravimetric and bench-scale analysis concurring with literature review and pointing towards reasonable kinetics and stability at temperatures on the order of 1500°C. A combined radiation, conduction, and species reaction/mass transport model was developed, utilizing Monte Carlo ray tracing, Lattice Boltzmann, and random walk particle tracking for the respective components to direct development and optimization of the reactor. With experimental data used for reaction rates, the model showed a path to efficiencies >20%, which could be market competitive with current PV-hydrolysis hydrogen generation systems. Economic analysis of a larger-scale plant (100kW modular system with cost performed at 500 modules) has been performed, assuming 0.5% and 10% internal rate of return. Without compression costs, H 2 production cost using this is technology at 12 USD/kg H 2 and 17 USD/kg H 2 for realized efficiencies of 20% and 15%, respectively.

14 SOLAR ENERGY↗