Search NASA⌕ Search

SEARCH · Search NASA

Results for “thermochemical processing”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

Characterization and properties of controlled nucleation thermochemical deposited /CNTD/ silicon carbide

Results are presented for an investigation designed to characterize the microstructure of controlled nucleation thermomechanical deposition (CNTD) produced SiC material with respect to grain structure, stoichiometry, phase analysis, etc., and to evaluate the room-temperature and high-temperature fracture and oxidation behavior. By using the CNTD process, ultrafine-grained SiC is deposited on tungsten wires as substrates, with superior surface smoothness and without the macrocolumnar growth commonly observed in conventional CVD materials. The results suggest that the high-purity, fully dense, and stable grain size SiC material produced by CNTD shows potential for high-temperature structural applications, provided that pertinent problems are resolved.

Dutta, S.↗
DOE OSTI2019

Exploring Molecular Mechanisms of Cosolvent Enhanced Biomass Deconstruction: An Overview of Recent Progress

In this chapter, we explore the mechanisms driving efficient thermochemical deconstruction and fractionation of lignocellulosic biomass in cosolvent mixtures for the production of biofuels and bioproducts. New approaches that combine molecular dynamics simulations with experimental characterization highlight the important role of cosolvents and their influence on molecular processes relevant to overcoming the natural recalcitrance of lignocellulose. From localized phase behavior on cellulose fibers to changes in lignin conformation, insights into cosolvent effects on biomass deconstruction involve understanding complex interactions between the solvent–solvent, solvent–substrate, and solvent–catalyst. Recently coordinated research efforts at multiple scales using computational tools, nano-scale imaging, and kinetic models have significantly advanced identification of high-performance cosolvents, shedding light on the mechanisms behind solvent-biomass interactions. Specifically, multifunctional cosolvents have been employed in leading biomass “solvolysis” technologies that favorably coordinate with dilute acids to solubilize and depolymerize all three primary biomass fractions of biomass: cellulose, hemicellulose, and lignin. As a result, recent work in studying solvent effects of multifunctional cosolvents has led to a paradigm shift toward the use of first principles to design biomass deconstruction techniques with the aim of maximizing total carbon utilization in biomass. The synergistic pairing of cosolvents with biomass deconstruction will lead scientists and engineers to overcome key technical and economic barriers of biomass processing, enabling a successful transition of the current energy landscape toward a future bioeconomy based on biomass as an alternative to petroleum.

Mostofian, Barmak↗
DOE OSTI2020

Thermochemical Insights into Stability and Hydration of Ion-Exchanged Zeolite ZK-5 (KFI Framework)

Extra-framework cations not only have a great impact on the structure of zeolites but also affect energetics and absorption of guest molecules. To investigate the stability and hydration of ion-exchanged zeolite ZK-5, high-temperature oxide melt solution calorimetry and direct water absorption calorimetry were used to reveal the influence of ion exchange on formation enthalpies and hydration processes. Formation enthalpies from oxides suggest that exchanging K + and Cs + with protons leads to destabilization of H-ZK-5, which is accompanied by the transition to an amorphous phase at high temperature. Water absorption and corresponding enthalpies are also affected by charge-compensating cations, for example, Na + ions in Na-ZK-5 promote the confinement of water molecules and generate higher water content and more exothermic absorption enthalpies. It is found that average ionic potentials are insufficient to explain formation enthalpies at different hydration levels, particularly for H-ZK-5 with complex cation forms. Instead, formation enthalpies from oxides generally become less exothermic as the distortion of the zeolite framework increases when replacing cations or absorbing/desorbing water molecules. Furthermore, this thermochemical study demonstrates the critical role of extra-framework cations and documents the complexity of ion exchange effects in zeolites with complicated topology and cation distribution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

BETO 2021 Peer Review - Analytical Development and Standardization for Biomass-Derived Thermochemical Liquids

This project began in FY14 to address the lack of standard chemical characterization analytical methods for bio-oils. Bio-oils are very complex and present numerous analytical challenges; yet reliable chemical information (quantification of both individual compounds and chemical functional groups) is needed to inform upgrading research and refinery co-processing. In this project, analysis needs are first determined from engaging the bioenergy community. Next, standard methods are developed to meet these needs, and then subsequently validated via inter-laboratory studies. Methods that are successfully validated (< 10% variability) are then shared as Laboratory Analytical Procedures (LAPs), which are free and publicly available. We have been tracking LAP use and have seen sustained usage as evidenced by an average of 500 pages views and 100 downloads per quarter, demonstrating the value of these methods to the bioenergy community. LAP methods that are particularly useful and reliable will be chosen for the next-level of standardization through ASTM. We have recently achieved approval by ASTM for our carbonyl titration method. This method (ASTM E3146) is the first example of an ASTM standard solely focused on the chemical characterization of bio-oils. Work in this project is meeting the analysis needs of the bioenergy community and will ultimately help enable the commoditization of bio-oils.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2014

Selective nano-patterning of graphene using a heated atomic force microscope tip

In this study, we introduce a selective thermochemical nano-patterning method of graphene on insulating substrates. A tiny heater formed at the end of an atomic force microscope (AFM) cantilever is optimized by a finite element method. The cantilever device is fabricated using conventional micromachining processes. After preliminary tests of the cantilever device, nano-patterning experiments are conducted with various conducting and insulating samples. The results indicate that faster scanning speed and higher contact force are desirable to reduce the sizes of nano-patterns. With the experimental condition of 1 μm/s and 24 mW, the heated AFM tip generates a graphene oxide layer of 3.6 nm height and 363 nm width, on a 300 nm thick SiO{sub 2} layer, with a tip contact force of 100 nN.

36 MATERIALS SCIENCE↗
DOE OSTI2017

High-Temperature Thermochemical Storage with Redox-Stable Perovskites for Concentrating Solar Power, CRADA Number: CRD-14-554

As part of a Federal Opportunity Announcement (FOA) Award, the project will be led by Colorado School of Mines (CSM) to explore and demonstrate the efficacy of highly reducible, redox-stable oxides to provide efficient thermochemical energy storage for heat release at temperatures of 900 degrees Celcius or more. NREL will support the material development for its application in a concentrating solar power (CSP) plant. In the project, NREL will provide its inventive system design, chemical looping for CSP, and use it as a platform to accommodate the chemical processes using a cost effective perovskite materials identified by CSM. NREL will design a 5-10kW particle receiver for perovskite reduction to store solar energy and help the development of a fluidized-bed reoxidation reactor and system integration. NREL will develop the demonstration receiver for on-sun test in the 5-10 kWt range in NREL's high flux solar furnace. NREL will assist in system analysis and provide techno-economic inputs for the overall system configuration.

14 SOLAR ENERGY↗
DOE OSTI2013

Transportation fuels from biomass via fast pyrolysis and hydroprocessing

Biomass is a renewable source of carbon, which could provide a means to reduce the greenhouse gas impact from fossil fuels in the transportation sector. Biomass is the only renewable source of liquid fuels, which could displace petroleum-derived products. Fast pyrolysis is a method of direct thermochemical conversion (non-bioconversion) of biomass to a liquid product. Although the direct conversion product, called bio-oil, is liquid; it is not compatible with the fuel handling systems currently used for transportation. Upgrading the product via catalytic processing with hydrogen gas, hydroprocessing, is a means that has been demonstrated in the laboratory. By this processing the bio-oil can be deoxygenated to hydrocarbons, which can be useful replacements of the hydrocarbon distillates in petroleum. While the fast pyrolysis of biomass is presently commercial, the upgrading of the liquid product by hydroprocessing remains in development, although it is moving out of the laboratory into scaled-up process demonstration systems.

bio-oil↗
DOE OSTI2012

Dual Layer Monolith ATR of Pyrolysis Oil for Distributed Synthesis Gas Production

We have successfully demonstrated a novel reactor technology, based on BASF dual layer monolith catalyst, for miniaturizing the autothermal reforming of pyrolysis oil to syngas, the second and most critical of the three steps for thermochemically converting biomass waste to liquid transportation fuel. The technology was applied to aged as well as fresh samples of pyrolysis oil derived from five different biomass feedstocks, namely switch-grass, sawdust, hardwood/softwood, golden rod and maple. Optimization of process conditions in conjunction with innovative reactor system design enabled the minimization of carbon deposit and control of the H2/CO ratio of the product gas. A comprehensive techno-economic analysis of the integrated process using in part, experimental data from the project, indicates (1) net energy recovery of 49% accounting for all losses and external energy input, (2) weight of diesel oil produced as a percent of the biomass to be ~14%, and (3) for a demonstration size biomass to Fischer-Tropsch liquid plant of ~ 2000 daily barrels of diesel, the price of the diesel produced is ~$\$$3.30 per gallon, ex. tax. However, the extension of catalyst life is critical to the realization of the projected economics. Catalyst deactivation was observed and the modes of deactivation, both reversible and irreversible were identified. An effective catalyst regeneration strategy was successfully demonstrated for reversible catalyst deactivation while a catalyst preservation strategy was proposed for preventing irreversible catalyst deactivation. Future work should therefore be focused on extending the catalyst life, and a successful demonstration of an extended (> 500 on-stream hours) catalyst life would affirm the commercial viability of the process.

09 BIOMASS FUELS↗
DOE OSTI2026

Elucidating key reducing species beyond ions in hydrogen plasma smelting reduction of iron ore

Hydrogen plasma smelting reduction (HPSR) of iron ore has attracted significant attention over the past decade due to its high-temperature operation, rapid plasma mediated reduction kinetics, and simpler density-based separation of molten iron product, compared to H2-based solid-state reduction. All of these attributes enable processing of low-grade ores for downstream use in electric-arc furnaces, as virgin iron with low gangue content is required for high quality steel and improved furnace operation. While positive ions exist within the plasma arc, this work demonstrates that near the anodic ore surface, hydrogen radicals and vibrationally excited hydrogen species dominate and their densities correlate well with observed reduction rates. Species concentrations in the transferred plasma arc and at the plasma-ore interface are evaluated using coupled thermal plasma and near-wall non-equilibrium plasma models. The thermal plasma model is validated against experimental voltage data and spectroscopic measurements of plasma temperature and density for varying current inputs. Modeling of the near surface thermochemical non-equilibrium and micrometer scale anode sheath layer reveals, in addition to the expected H + , significant concentrations of ArH + and H$^+_3$ ions, typically not observed in thermal plasmas under thermodynamic equilibrium. Our results show that the inverted sheath structure at the anodic ore surface strongly suppresses reactive positive ion fluxes, while non-equilibrium electron-impact processes generate abundant hydrogen radicals and vibrationally excited species. These findings highlight the critical role of non-equilibrium effects in hydrogen arc-driven iron ore reduction and advance understanding beyond prevailing hypotheses centered on hydrogen ion-driven mechanisms.

08 HYDROGEN↗
DOE OSTI2026

Biomass Demineralization: A Critical Need for Future Biorefineries

Biomass contains up to 14 essential elements that serve as nutrients for plant growth and development, including photosynthesis and enzyme functionalities. These elements in different chemical forms (e.g., minerals) constitute the inorganic fraction of biomass and can cause operational issues in thermal and biochemical biomass conversion technologies. In biomass gasification and pyrolysis processes, for instance, inorganics can cause fouling, tar formation, and corrosion. In catalytic and biochemical processes, inorganics can poison catalysts, alter biochemical pathways, and modify product yields and selectivity. This review provides an overview of the inorganic content in biomass feedstocks, the critical role inorganics play in plant biochemistry, the effect that inorganics have in various thermochemical and biochemical biomass conversion technologies, and different approaches to remove them from biomass. We provide recommendations for future research, focusing on developing technologies to effectively remove inorganics from biomass, using the inorganics to improve soil quality and for alternative applications, and designing biorefineries to convert demineralized biomass obtained from diverse sources.

09 - BIOMASS FUELS↗
DOE OSTI2016

Sustainable Ammonia Synthesis – Exploring the scientific challenges associated with discovering alternative, sustainable processes for ammonia production

Ammonia (NH 3 ) is essential to all life on our planet. Until about 100 years ago, NH 3 produced by reduction of dinitrogen (N 2 ) in air came almost exclusively from bacteria containing the enzyme nitrogenase.. DOE convened a roundtable of experts on February 18, 2016. Participants in the Roundtable discussions concluded that the scientific basis for sustainable processes for ammonia synthesis is currently lacking, and it needs to be enhanced substantially before it can form the foundation for alternative processes. The Roundtable Panel identified an overarching grand challenge and several additional scientific grand challenges and research opportunities: -Discovery of active, selective, scalable, long-lived catalysts for sustainable ammonia synthesis. -Development of relatively low pressure (<10 atm) and relatively low temperature (<200 C) thermal processes. -Integration of knowledge from nature (enzyme catalysis), molecular/homogeneous and heterogeneous catalysis. -Development of electrochemical and photochemical routes for N 2 reduction based on proton and electron transfer -Development of biochemical routes to N 2 reduction -Development of chemical looping (solar thermochemical) approaches -Identification of descriptors of catalytic activity using a combination of theory and experiments -Characterization of surface adsorbates and catalyst structures (chemical, physical and electronic) under conditions relevant to ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Editorial: Biomass Modification, Characterization, and Process Monitoring Analytics to Support Biofuel and Biomaterial Production

This Frontiers Research Topic journeys through various challenges facing researchers seeking to develop fuels and products derived from lignocellulosic biomass. These challenges include: the rapid quantification of plant cell wall chemistry, enabling yields of potential monomeric sugars to be assessed, identification of plants possessing ideal trait that can be brought to the forefront of research efforts; once the native plant chemistry is known, how can yields be improved by chemically or genetically altering plant cell walls to reduce recalcitrance; does genetic modification of plants to increase accessibility to saccharification enzymes hinder the plant’s growth and/or function; are the innovative methods identified by researchers cost-effective and scalable to a commercial level? These topics are a sampling of the obstacles researchers combat when nominating a specific plant for downstream applications or implementing new deconstruction, genetic, or measurement strategies. How well can different plants can be broken down into useful, downstream precursor molecules? Efforts to develop a lucid picture of the chemical composition of abundant, diverse plants being explored as potential starting feedstocks has resulted in the evolution of high-throughput techniques that permit many more samples to be screened in much shorter periods of time. Advances in thermochemical and spectroscopic techniques have enabled the screening of thousands of plants for different phenotypes, such as cell-wall composition and monomeric sugar release. Some instrumental methods have been coupled with multivariate analysis, providing elegant chemometric predictive models enabling the accelerated identification of potential feedstocks. Rapid instrumental techniques have been developed for real-time monitoring of diverse processes, such as the efficacy of specific pretreatment strategies, or downstream products, such as biofuels and biomaterials. Real-time process monitoring techniques are needed for all stages of the feedstocks-to-biofuels conversion process to maximize efficiency and lower costs by monitoring and optimizing performance. These approaches allow researchers to adjust experimental conditions during, rather than at the conclusion, of processes, thereby decreasing overhead expenses.

09 BIOMASS FUELS↗
DOE OSTI2024

The role of stereochemistry in combustion processes

Stereochemical effects significantly influence chemical processes, yet it is not well understood if they are a leading source of uncertainty in combustion modeling. Stereochemistry influences a combustion model (i) at the earliest stage of its construction when mapping the reaction network, (ii) in the computation of individual thermochemical and rate parameters, and (iii) in the prediction of combustion observables. The present work reviews the importance of enumerating stereochemical species and reactions at each of these steps. Further, it analyzes the separate influence of several types of stereochemistry, including geometric, optical, and fleeting transition state diastereomers. Three reaction networks serve to examine which stages of low-temperature oxidation are most affected by stereochemistry, including the first and second oxidation of n-butane, the third oxidation of n-pentane, and the early stages of pyrolysis of 1- and 2-pentene. The 149 reactions in the n-butane mechanism are expanded to 183 reactions when accounting for diastereomerism. Each of these 183 reactions is parameterized with ab initio kinetics computations to determine that, for the n-butane mechanism, the median factor of diastereomeric deviation is 3.5 at 360 K for rate constants and as high as 1.6 for mechanism reactivity, in terms of ignition delay times, as opposed to a mechanism without stereochemical expansion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Deprotonated Dicarboxylic Acid Homodimers: Hydrogen Bonds and Atmospheric Implications

Dicarboxylic acids represent an important class of water-soluble organic compounds found in the atmosphere. In this work we are studying properties of dicarboxylic acid homodimer complexes (HO 2 (CH 2 ) n CO 2 - [HO 2 (CH 2 ) n CO 2 H], n = 0-12), as potentially important intermediates in aerosol formation processes. Our approach is based on experimental data from negative ion photoelectron spectra of the dimer complexes combined with updated measurements of the corresponding monomer species. These results are analyzed with quantum-mechanical calculations, which provide further information about equilibrium structures, thermochemical parameters associated with the complex formation, and evaporation rates. We find that upon formation of the dimer complexes the electron binding energies increase by 1.3–1.7 eV (30.0–39.2 kcal/mol), indicating increased stability of the dimerized complexes. Calculations indicate that these dimer complexes are characterized by the presence of strong intermolecular hydrogen bonds with high binding energies and are thermodynamically favorable to form with low evaporation rates. Comparison with previously studied HSO 4 - [HO 2 (CH 2 ) 2 CO 2 H] complex (J. Phys. Chem. Lett. 2013, 4, 779-785) shows that HO 2 (CH 2 ) 2 CO 2 - [HO 2 (CH 2 ) 2 CO 2 H] has very similar thermochemical properties. These results imply that dicarboxylic acids not only can contribute to the heterogeneous complexes formation involving sulfuric acid and dicarboxylic acids, but also can promote the formation of homogenous complexes by involving dicarboxylic acids themselves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Substituted SrFeO 3 as robust oxygen sorbents for thermochemical air separation: correlating redox performance with compositional and structural properties

Thermochemical air separation via cyclic redox reactions of oxide-based oxygen sorbents has the potential to achieve high energy efficiency. Although a number of promising sorbents have been investigated, further improvements in sorbent performance through a fundamental understanding of the structure–performance relationships are highly desirable. In this study, we systematically investigated the effects of A and B site dopants on the oxygen uptake/release properties (i.e., vacancy formation energy, reduction enthalpy, oxygen release temperature, and oxygen capacity) of the SrFeO 3 family of perovskites as oxygen sorbents. A monotonic correlation between DFT calculated oxygen vacancy formation energy and oxygen release temperature demonstrates the effectiveness of DFT for guiding sorbent selection. Combining vacancy formation energy with stability analysis, dopants such as Ba and Mn have been identified for tuning the redox property of SrFeO 3 sorbents, and increasing the oxygen capacity for temperature and pressure swings when compared to undoped SrFeO 3 . The Mn doped sample proved to be highly stable, with less than a 3% decrease in capacity over 1000 cycles. Although the dynamic nature of the redox process makes it difficult to use a single vacancy formation energy as the descriptor, a systematic approach was developed to correlate the oxygen storage capacities with the sorbents’ compositional properties and vacancy formation energies. The combination of DFT calculations with experimental studies from this study provides a potentially effective strategy for developing improved sorbents for thermochemical air separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

New Thermochemical Salt Hydrate System for Energy Storage in Buildings

This paper introduces an innovative design for an “inorganic salt-expanded graphite” composite thermochemical system. The storage unit is made of a perforated, compressed, expanded graphite block impregnated with molten CaCl 2 ∙6H 2 O; the humid air passes through the holes that allow the moisture to diffuse and react with the salt. The prepared block underwent 90 hydration-dehydration cycles. Although most of the performed cycles were carried out with salt overhydration and deliquescence, the treated samples have remained mechanically and thermally stable with no drop in energy density. The volumetric energy density of the composite ranged from 135.5 to 277.6 kWh/m 3 , depending on airflow rate and absolute humidity. To ensure composite material cycling stability, the energy density of the block was measured during hydration at similar conditions of absolute humidity, inlet temperature, and airflow rate (0.01 kg water /kg air , 20 °C, 400 l/min). The average energy density at these conditions was sustained at 219 kWh/m 3 . The block integrity was monitored by visual inspection after removing it from the reactor chamber every few cycles. Both the composite material and its manufacturing process are simple and easy to scale up for future commercialization.

25 ENERGY STORAGE↗
NASA NTRS2000

A Study of Upgraded Phenolic Curing for RSRM Nozzle Rings

A thermochemical cure model for predicting temperature and degree of cure profiles in curing phenolic parts was developed, validated and refined over several years. The model supports optimization of cure cycles and allows input of properties based upon the types of material and the process by which these materials are used to make nozzle components. The model has been refined to use sophisticated computer graphics to demonstrate the changes in temperature and degree of cure during the curing process. The effort discussed in the paper will be the conversion from an outdated solid modeling input program and SINDA analysis code to an integrated solid modeling and analysis package (I-DEAS solid model and TMG). Also discussed will be the incorporation of updated material properties obtained during full scale curing tests into the cure models and the results for all the Reusable Solid Rocket Motor (RSRM) nozzle rings.

Smartt, Ziba↗
DOE OSTI2021

Recent Advancements in Catalytic Fast Pyrolysis for the Production of Fuels and Chemicals from Biomass

Catalytic fast pyrolysis (CFP) is a promising biorefinery technology platform for generating both fuel blendstocks and chemical co-products. The versatility of this platform is afforded by (1) the coupling of a thermochemical deconstruction step to a catalytic step that enables tuning of the product slate and (2) the diversity of accessible products across gaseous, liquid, and solid streams. However, there are a number of challenges impeding commercial viability for this CFP platform, including high process costs caused by low carbon efficiency to bio-oil due to coking and light gas formation, the quality and properties of the bio-oil dictate processability for downstream operations, and the heterogeneity of the bio-oil limits quality of resulting fuel blendstocks. This presentation will discuss our efforts to address these challenges through a combined experimental-computational approach to catalyst design and process development, with a specific focus on (1) modifying product composition through catalyst design and (2) generating olefinic and oxygenated chemical co-products.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗