The NATA code: Theory and analysis, volume 1. [user manuals (computer programming) - gas dynamics, wind tunnels

NASA Technical Reports Server (NTRS)

Bade, W. L.; Yos, J. M.

1975-01-01

A computer program for calculating quasi-one-dimensional gas flow in axisymmetric and two-dimensional nozzles and rectangular channels is presented. Flow is assumed to start from a state of thermochemical equilibrium at a high temperature in an upstream reservoir. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. Electronic nonequilibrium effects can be included using a two-temperature model. An approximate laminar boundary layer calculation is given for the shear and heat flux on the nozzle wall. Boundary layer displacement effects on the inviscid flow are considered also. Chemical equilibrium and transport property calculations are provided by subroutines. The code contains precoded thermochemical, chemical kinetic, and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It provides calculations of the stagnation conditions on axisymmetric or two-dimensional models, and of the conditions on the flat surface of a blunt wedge. The primary purpose of the code is to describe the flow conditions and test conditions in electric arc heated wind tunnels.

CFD studies on biomass thermochemical conversion.

PubMed

Wang, Yiqun; Yan, Lifeng

2008-06-01

Thermochemical conversion of biomass offers an efficient and economically process to provide gaseous, liquid and solid fuels and prepare chemicals derived from biomass. Computational fluid dynamic (CFD) modeling applications on biomass thermochemical processes help to optimize the design and operation of thermochemical reactors. Recent progression in numerical techniques and computing efficacy has advanced CFD as a widely used approach to provide efficient design solutions in industry. This paper introduces the fundamentals involved in developing a CFD solution. Mathematical equations governing the fluid flow, heat and mass transfer and chemical reactions in thermochemical systems are described and sub-models for individual processes are presented. It provides a review of various applications of CFD in the biomass thermochemical process field.

CFD Studies on Biomass Thermochemical Conversion

PubMed Central

Wang, Yiqun; Yan, Lifeng

2008-01-01

Thermochemical conversion of biomass offers an efficient and economically process to provide gaseous, liquid and solid fuels and prepare chemicals derived from biomass. Computational fluid dynamic (CFD) modeling applications on biomass thermochemical processes help to optimize the design and operation of thermochemical reactors. Recent progression in numerical techniques and computing efficacy has advanced CFD as a widely used approach to provide efficient design solutions in industry. This paper introduces the fundamentals involved in developing a CFD solution. Mathematical equations governing the fluid flow, heat and mass transfer and chemical reactions in thermochemical systems are described and sub-models for individual processes are presented. It provides a review of various applications of CFD in the biomass thermochemical process field. PMID:19325848

Syngas Production By Thermochemical Conversion Of H2o And Co2 Mixtures Using A Novel Reactor Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearlman, Howard; Chen, Chien-Hua

The Department of Energy awarded Advanced Cooling Technologies, Inc. (ACT) an SBIR Phase II contract (#DE-SC0004729) to develop a high-temperature solar thermochemical reactor for syngas production using water and/or carbon dioxide as feedstocks. The technology aims to provide a renewable and sustainable alternative to fossil fuels, promote energy independence and mitigate adverse issues associated with climate change by essentially recycling carbon from carbon dioxide emitted by the combustion of hydrocarbon fuels. To commercialize the technology and drive down the cost of solar fuels, new advances are needed in materials development and reactor design, both of which are integral elements inmore » this program.« less

Judy Netter | NREL

Science.gov Websites

thermochemical reactions (primarily hydrogen production), and recently Solar Power Tower Receiver design. She has . Her expertise involves the design and fabrication of prototype experimental equipment along with the programs and controls. CSP-related projects include the design of experiments and test equipment for

Daniel Carpenter | NREL

Science.gov Websites

Daniel.Carpenter@nrel.gov | 303-384-6709 Orcid ID http://orcid.org/0000-0001-7625-9308 Research Interests Impact of ), especially related to blending low-cost, sustainable feedstocks into the biofuels supply chain Design thermochemical and catalytic experimental reactor systems Affiliated Research Programs Feedstocks (PI) Biomass

Mark F. Davis | NREL

Science.gov Websites

| 303-384-6140 Orcid ID http://orcid.org/0000-0003-4541-9852 Research Interests Dr. Mark Davis is the years, he has served as the Platform Program Manager for Thermochemical and has directed research Science Center, including high throughput recalcitrance assays, omics research, computational modeling

Microcomputer Calculation of Thermodynamic Properties from Molecular Parameters of Gases.

ERIC Educational Resources Information Center

Venugopalan, Mundiyath

1990-01-01

Described in this article is a problem-solving activity which integrates the application of microcomputers with the learning of physical chemistry. Students use the program with spectroscopic data to calculate the thermodynamic properties and compare them with the values from the thermochemical tables. (Author/KR)

System and process for producing fuel with a methane thermochemical cycle

DOEpatents

Diver, Richard B.

2015-12-15

A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

Thermochemical Conversion: Using Heat and Catalysts to Make Biofuels and Bioproducts

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

2013-07-29

This fact sheet discusses the Bioenergy Technologies Office's thermochemical conversion critical technology goal. And, how through the application of heat, robust thermochemical processes can efficiently convert a broad range of biomass.

Fundamentals of the NEA Thermochemical Database and its influence over national nuclear programs on the performance assessment of deep geological repositories.

PubMed

Ragoussi, Maria-Eleni; Costa, Davide

2017-03-14

For the last 30 years, the NEA Thermochemical Database (TDB) Project (www.oecd-nea.org/dbtdb/) has been developing a chemical thermodynamic database for elements relevant to the safety of radioactive waste repositories, providing data that are vital to support the geochemical modeling of such systems. The recommended data are selected on the basis of strict review procedures and are characterized by their consistency. The results of these efforts are freely available, and have become an international point of reference in the field. As a result, a number of important national initiatives with regard to waste management programs have used the NEA TDB as their basis, both in terms of recommended data and guidelines. In this article we describe the fundamentals and achievements of the project together with the characteristics of some databases developed in national nuclear waste disposal programs that have been influenced by the NEA TDB. We also give some insights on how this work could be seen as an approach to be used in broader areas of environmental interest. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermochemical reactor systems and methods

DOEpatents

Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

2016-11-29

Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

A thermochemical-biochemical hybrid processing of lignocellulosic biomass for producing fuels and chemicals.

PubMed

Shen, Yanwen; Jarboe, Laura; Brown, Robert; Wen, Zhiyou

2015-12-01

Thermochemical-biological hybrid processing uses thermochemical decomposition of lignocellulosic biomass to produce a variety of intermediate compounds that can be converted into fuels and chemicals through microbial fermentation. It represents a unique opportunity for biomass conversion as it mitigates some of the deficiencies of conventional biochemical (pretreatment-hydrolysis-fermentation) and thermochemical (pyrolysis or gasification) processing. Thermochemical-biological hybrid processing includes two pathways: (i) pyrolysis/pyrolytic substrate fermentation, and (ii) gasification/syngas fermentation. This paper provides a comprehensive review of these two hybrid processing pathways, including the characteristics of fermentative substrates produced in the thermochemical stage and microbial utilization of these compounds in the fermentation stage. The current challenges of these two biomass conversion pathways include toxicity of the crude pyrolytic substrates, the inhibition of raw syngas contaminants, and the mass-transfer limitations in syngas fermentation. Possible approaches for mitigating substrate toxicities are discussed. The review also provides a summary of the current efforts to commercialize hybrid processing. Copyright © 2015 Elsevier Inc. All rights reserved.

Thermochemical Conversion Techno-Economic Analysis | Bioenergy | NREL

Science.gov Websites

Conversion Techno-Economic Analysis Thermochemical Conversion Techno-Economic Analysis NREL's Thermochemical Conversion Analysis team focuses on the conceptual process design and techno-economic analysis , detailed process models, and TEA developed under this project provide insights into the potential economic

A review of cryogenic testing performed by the thermochemical test branch, Manned Spacecraft Center in support of Apollo 13 and14

NASA Technical Reports Server (NTRS)

Propp, C. E.; Mcgee, J. M.

1971-01-01

The Apollo 13 anomaly provided considerable impetus for a variety of types of cryogenic and ignition tests. The logic of the various test program designs, the test techniques, and their final impact upon the investigation findings are described. In addition, several test programs initiated to determine the thermal performance and general performance characteristics of the redesigned Apollo 14 cryogenic storage system are presented.

A program for calculating expansion-tube flow quantities for real-gas mixtures and comparison with experimental results

NASA Technical Reports Server (NTRS)

Miller, C. G., III

1972-01-01

A computer program written in FORTRAN 4 language is presented which determines expansion-tube flow quantities for real test gases CO2 N2, O2, Ar, He, and H2, or mixtures of these gases, in thermochemical equilibrium. The effects of dissociation and first and second ionization are included. Flow quantities behind the incident shock into the quiescent test gas are determined from the pressure and temperature of the quiescent test gas in conjunction with: (1) incident-shock velocity, (2) static pressure immediately behind the incident shock, or (3) pressure and temperature of the driver gas (imperfect hydrogen or helium). The effect of the possible existence of a shock reflection at the secondary diaphragm of the expansion tube is included. Expansion-tube test-section flow conditions are obtained by performing an isentropic unsteady expansion from the conditions behind the incident shock or reflected shock to either the test-region velocity or the static pressure. Both a thermochemical-equilibrium expansion and a frozen expansion are included. Flow conditions immediately behind the bow shock of a model positioned at the test section are also determined. Results from the program are compared with preliminary experimental data obtained in the Langley 6-inch expansion tube.

Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment

Treesearch

Shishir P. S. Chundawat; Bryon S. Donohoe; Leonardo da Costa Sousa; Thomas Elder; Umesh P. Agarwal; Fachuang Lu; John Ralph; Michael E. Himmel; Venkatesh Balan; Bruce E. Dale

2011-01-01

Deconstruction of lignocellulosic plant cell walls to fermentable sugars by thermochemical and/or biological means is impeded by several poorly understood ultrastructural and chemical barriers. A promising thermochemical pretreatment called ammonia fiber expansion (AFEX) overcomes the native recalcitrance of cell walls through subtle morphological and physicochemical...

Cesium Neonide: Molecule or Thermochemical Exercise?

ERIC Educational Resources Information Center

Blake, P. G.; Clack, D. W.

1982-01-01

Thermochemical cycles are used to decide which hypothetical compounds might exist and, if not, what is the factor that condemns them to non-existence. Hypothetical compounds of rare gases provide examples of the approach with added historical interest that thermochemical considerations led to prediction and demonstration that XePtF-6 was stable.…

Search for New Highly Energetic Phases under Compression and Shear

DTIC Science & Technology

2015-05-01

bar barn British thermal unit (thermochemical) calorie (thermochemical) cal (thermochemical/cm ) curie degree (angle) degree Fahrenheit...corresponding finite element algorithms and subroutines are developed. (c) Problems on compression and shear of a sample in rotational diamond anvil...element algorithms and subroutines are developed. Model problems on martensitic microstructure evolution are solved. (f) Experimental approaches to study

Controlled Chemical Patterns with ThermoChemical NanoLithography (TCNL)

NASA Astrophysics Data System (ADS)

Carroll, Keith; Giordano, Anthony; Wang, Debin; Kodali, Vamsi; King, W. P.; Marder, S. R.; Riedo, E.; Curtis, J. E.

2012-02-01

Many research areas, both fundamental and applied, rely upon the ability to organize non-trivial assemblies of molecules on surfaces. In this work, we introduce a significant extension of ThermoChemical NanoLithography (TCNL), a high throughput chemical patterning technique that uses temperature-driven chemical reactions localized near the tip of a thermal cantilever. By combining a chemical kinetics based model with experiments, we have developed a protocol for varying the concentration of surface bound molecules. The result is an unprecedented ability to fabricate extremely complex patterns comprised of varying chemical concentrations, as demonstrated by sinusoidal patterns of amine groups with varying pitches (˜5-15 μm) and the replication of Leonardo da Vinci's Mona Lisa with dimensions of ˜30 x 40 μm^2. Programmed control of the chemical reaction rate should have widespread applications for a technique which has already been shown to nanopattern various substrates including graphene nanowires, piezoelectric crystals, and optoelectronic materials.

Study of the formation of thermochemical laser-induced periodic surface structures on Cr, Ti, Ni and NiCr films under femtosecond irradiation

NASA Astrophysics Data System (ADS)

Dostovalov, A. V.; Korolkov, V. P.; Terentyev, V. S.; Okotrub, K. A.; Dultsev, F. N.; Babin, S. A.

2017-07-01

The formation of femtosecond laser-induced periodic surface structures (LIPSS's) on Cr, Ti, Ni and NiCr films (with different Cr contents) is investigated. It is established that thermochemical LIPSS's with periods of 950, 930 and 980 nm are formed, respectively, on the surfaces of titanium, chromium, and nichrome (with a chromium content of 20%); however, thermochemical LIPSS's are not formed on the surfaces of nickel and nichrome with a low chromium content, although Raman data indicate that oxidation occurs in all cases. A weakly ordered ablated structure with a period of 250-300 nm is found to be formed on oxidised areas of thermochemical LIPSS's in the case of chromium and nichrome (80/20). Experimental data on selective etching of thermochemical LIPSS's on titanium and chromium films are presented.

Thermochemical conversion of biomass storage covers to reduce ammonia emissions from dairy manure Thermochemical conversion of biomass storage covers to reduce ammonia emissions from dairy manure

USDA-ARS?s Scientific Manuscript database

Manure storages, and in particular those storing digested manure, are a source of ammonia (NH3) emissions. Permeable manure storage covers can reduce NH3 emissions, however performance can decline as they degrade. Thermochemical conversion of biomass through pyrolysis and steam treatment could incre...

Evaluation of chemical, thermobaric and thermochemical pre-treatment on anaerobic digestion of high-fat cattle slaughterhouse waste.

PubMed

Harris, Peter W; Schmidt, Thomas; McCabe, Bernadette K

2017-11-01

This work aimed to enhance the anaerobic digestion of fat-rich dissolved air flotation (DAF) sludge through chemical, thermobaric, and thermochemical pre-treatment methods. Soluble chemical oxygen demand was enhanced from 16.3% in the control to 20.84% (thermobaric), 40.82% (chemical), and 50.7% (thermochemical). Pre-treatment altered volatile fatty acid concentration by -64% (thermobaric), 127% (chemical) and 228% (thermochemical). Early inhibition was reduced by 20% in the thermochemical group, and 100% in the thermobaric group. Specific methane production was enhanced by 3.28% (chemical), 8.32% (thermobaric), and 8.49% (thermochemical) as a result of pre-treatment. Under batch digestion, thermobaric pre-treatment demonstrated the greatest improvement in methane yield with respect to degree of pre-treatment applied. Thermobaric pre-treatment was also the most viable for implementation at slaughterhouses, with potential for heat-exchange to reduce pre-treatment cost. Further investigation into long-term impact of pre-treatments in semi-continuous digestion experiments will provide additional evaluation of appropriate pre-treatment options for high-fat slaughterhouse wastewater. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Chemical state of chromium in sewage sludge ash based phosphorus-fertilisers.

PubMed

Vogel, Christian; Adam, Christian; Kappen, Peter; Schiller, Tara; Lipiec, Ewelina; McNaughton, Don

2014-05-01

Sewage sludge ash (SSA) based P-fertilisers were produced by thermochemical treatment of SSA with Cl-donors at approximately 1000°C. During this thermochemical process heavy metals are separated as heavy metal chlorides via the gas phase. Chromium cannot be separated under normal conditions. The risk of the development of toxic Cr(VI) during the thermochemical process was investigated. X-ray Absorption Spectroscopy measurements showed that SSA and thermochemically treated SSA with CaCl2, MgCl2 and NaCl contain Cr(III) compounds only. In contrast, treating SSA with elevated quantities of Na2CO3, to enhance the plant-availability of the phosphate phases of the fertiliser, developed approximately 10-15% Cr(VI). Furthermore, Raman microspectroscopy showed that using Mg-carbonate reduces the risk of a Cr(VI) development during thermochemical treatment. Additionally, leaching tests showed that only a Cr-water solubility>10% is an indicator for Cr(VI) in SSA based P-fertilisers. Copyright © 2013 Elsevier Ltd. All rights reserved.

An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

NASA Technical Reports Server (NTRS)

Chao, R. E.; Cox, K. E.

1975-01-01

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.

Thermochemical analyses of the oxidative vaporization of metals and oxides by oxygen molecules and atoms

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Leisz, D. M.; Fryburg, G. C.; Stearns, C. A.

1977-01-01

Equilibrium thermochemical analyses are employed to describe the vaporization processes of metals and metal oxides upon exposure to molecular and atomic oxygen. Specific analytic results for the chromium-, platinum-, aluminum-, and silicon-oxygen systems are presented. Maximum rates of oxidative vaporization predicted from the thermochemical considerations are compared with experimental results for chromium and platinum. The oxidative vaporization rates of chromium and platinum are considerably enhanced by oxygen atoms.

Observations and Thermochemical Calculations for Hot-Jupiter Atmospheres

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver; Cubillos, Patricio; Stemm, Madison

2015-01-01

I present Spitzer eclipse observations for WASP-14b and WASP-43b, an open source tool for thermochemical equilibrium calculations, and components of an open source tool for atmospheric parameter retrieval from spectroscopic data. WASP-14b is a planet that receives high irradiation from its host star, yet, although theory does not predict it, the planet hosts a thermal inversion. The WASP-43b eclipses have signal-to-noise ratios of ~25, one of the largest among exoplanets. To assess these planets' atmospheric composition and thermal structure, we developed an open-source Bayesian Atmospheric Radiative Transfer (BART) code. My dissertation tasks included developing a Thermochemical Equilibrium Abundances (TEA) code, implementing the eclipse geometry calculation in BART's radiative transfer module, and generating parameterized pressure and temperature profiles so the radiative-transfer module can be driven by the statistical module.To initialize the radiative-transfer calculation in BART, TEA calculates the equilibrium abundances of gaseous molecular species at a given temperature and pressure. It uses the Gibbs-free-energy minimization method with an iterative Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. The code is tested against the original method developed by White at al. (1958), the analytic method developed by Burrows and Sharp (1999), and the Newton-Raphson method implemented in the open-source Chemical Equilibrium with Applications (CEA) code. TEA, written in Python, is modular, documented, and available to the community via the open-source development site GitHub.com.Support for this work was provided by NASA Headquarters under the NASA Earth and Space Science Fellowship Program, grant NNX12AL83H, by NASA through an award issued by JPL/Caltech, and through the Science Mission Directorate's Planetary Atmospheres Program, grant NNX12AI69G.

Biomass energy: a monograph

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hiler, E.A.; Stout, B.A.

1985-01-01

This monograph presents a review of the status of biomass as an alternative energy source, with particular emphasis on the energy research programs of the Texas A and M University System. Eight chapters include joint research efforts in thermochemical conversion (combustion, gasification, pyrolysis), biological conversion (anaerobic digestion, fermentation), and plant oil extraction (physical expelling, solvent extraction). Six chapters are indexed separately for inclusion in the Energy Data Base and in Energy Abstracts for Policy Analysis.

A Working Model for the System Alumina-Magnesia.

DTIC Science & Technology

1983-05-01

Several regions in the resulting diagram appear rather uncertain: the liquidus ’National bureau of StandaTds. JANAF Thermochemical Tables, by D. R. Stull ...Code 131) 1 Naval Ordnance Station, Indian Head (Technical Library) 29 Naval Postgraduate School. Monterey Code 012, Dean of Research (1) Code 06... Dean of Science and Engineering (1) Code 1424. Library - Technical Reports (2) Code 33. Weapons Engineering Program Office (1) Code 61. Chairman

Independent Assessment of Technology Characterizations to Support the Biomass Program Annual State-of-Technology Assessments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeh, B.

2011-03-01

This report discusses an investigation that addressed two thermochemical conversion pathways for the production of liquid fuels and addressed the steps to the process, the technology providers, a method for determining the state of technology and a tool to continuously assess the state of technology. This report summarizes the findings of the investigation as well as recommendations for improvements for future studies.

Thermochemical Production of Hydrogen from Water.

ERIC Educational Resources Information Center

Bamberger, C. E.; And Others

1978-01-01

Discusses the possible advantages of decomposing water by means of thermochemical cycles. Explains that, if energy consumption can be minimized, this method is capable of producing hydrogen more efficiently than electrolysis. (GA)

WATEQF; a FORTRAN IV version of WATEQ : a computer program for calculating chemical equilibrium of natural waters

USGS Publications Warehouse

Plummer, Niel; Jones, Blair F.; Truesdell, Alfred Hemingway

1976-01-01

WATEQF is a FORTRAN IV computer program that models the thermodynamic speciation of inorganic ions and complex species in solution for a given water analysis. The original version (WATEQ) was written in 1973 by A. H. Truesdell and B. F. Jones in Programming Language/one (PL/1.) With but a few exceptions, the thermochemical data, speciation, coefficients, and general calculation procedure of WATEQF is identical to the PL/1 version. This report notes the differences between WATEQF and WATEQ, demonstrates how to set up the input data to execute WATEQF, provides a test case for comparison, and makes available a listing of WATEQF. (Woodard-USGS)

Computer-Aided Process Model For Carbon/Phenolic Materials

NASA Technical Reports Server (NTRS)

Letson, Mischell A.; Bunker, Robert C.

1996-01-01

Computer program implements thermochemical model of processing of carbon-fiber/phenolic-matrix composite materials into molded parts of various sizes and shapes. Directed toward improving fabrication of rocket-engine-nozzle parts, also used to optimize fabrication of other structural components, and material-property parameters changed to apply to other materials. Reduces costs by reducing amount of laboratory trial and error needed to optimize curing processes and to predict properties of cured parts.

Hypersonic, nonequilibrium flow over the FIRE 2 forebody at 1634 sec

NASA Technical Reports Server (NTRS)

Chambers, Lin Hartung

1994-01-01

The numerical simulation of hypersonic flow in thermochemical nonequilibrium over the forebody of the FIRE 2 vehicle at 1634 sec in its trajectory is described. The simulation was executed on a Cray C90 with the program Langley Aerodynamic Upwind Relaxation Algorithm (LAURA) 4.0.2. Code setup procedures and sample results, including grid refinement studies, are discussed. This simulation relates to a study of radiative heating predictions on aerobrake type vehicles.

Constraints on core-mantle boundary topography from models of thermal and thermochemical convection

NASA Astrophysics Data System (ADS)

Deschamps, Frédéric; Rogister, Yves; Tackley, Paul J.

2018-01-01

Mantle flow induces dynamic topography at the core-mantle boundary (CMB), with distribution and amplitude that depend on details of the flow. To assess whether observations of CMB topography can give constraints on deep mantle structure, we determine CMB dynamic topography associated with different models of mantle convection, including thermochemical and purely thermal models. We investigate the influence of key controlling parameters, specifically the thermal viscosity ratio (ΔηT) and, for thermochemical models, the density contrast (ΔρC) and viscosity ratio (ΔηC) between primordial and regular materials. In purely thermal models, plume clusters induce positive topography with an amplitude that decreases with increasing ΔηT. In thermochemical models with moderate density contrasts, around 100-200 kg m-3, reservoirs of dense material induce depressions in CMB topography, surrounded by a ridge of positive topography. The average depression depth and ridge height increase with increasing ΔρC and ΔηC, but decrease with increasing ΔηT. We find that for purely thermal models or thermochemical models with ΔρC ˜ 90 kg m-3 and less, the long-wavelength (spherical harmonic degrees up to l = 4) dynamic topography and shear wave velocity anomalies predicted by thermochemical distributions anticorrelate. By contrast, for models with ΔρC ≥ 100 kg m-3 and ΔηC > 1, long-wavelength dynamic topography and shear wave velocity anomalies correlate well. This potentially provides a test to infer the nature, that is, either purely or mostly thermal (ΔρC ≤ 100 kg m-3 m-3) or strongly thermochemical (ΔρC ≥ 100 kg m-3), of the low shear wave velocity provinces observed by global tomographic images. The presence of post-perovskite, provided that its viscosity is similar to that of bridgmanite, does not alter these conclusions.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

NASA Astrophysics Data System (ADS)

Lany, Stephan

2018-02-01

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Influence of the Stefan Flow on Heat Transfer in the System "Gas-Solid Particle" in Thermochemical Conversion of a Solid Fuel

NASA Astrophysics Data System (ADS)

Pechenegov, Yu. Ya.; Mrakin, A. N.

2017-09-01

Recommendations are presented on calculating interphase heat transfer in gas-disperse systems of plants for thermochemical conversion of ground solid fuel. An analysis is made of the influence of the gas release of fuel particles on the heat transfer during their heating. It is shown that in the processes of thermal treatment of oil shales, the presence of gas release reduces substantially the intensity of interphase heat transfer compared to the heat transfer in the absence of thermochemical decomposition of the solid phase.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

DOE PAGES

Lany, Stephan

2018-02-21

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lany, Stephan

The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.

Thermochemical energy storage: Proceedings from the International Seminar on hermochemical Energy Storage

NASA Astrophysics Data System (ADS)

Wettermark, G.

1980-10-01

Energy storage problems are explored. Tomorrow's energy sources will provide a continuous flow of energy. Matching supply and demand will necessitate a wide range of storage capabilities. For storing heat thermochemical and economic solutions may take advantage of the various options inherent in this kind of storage, namely heat pumping, transport of heat and direct conversion to other desired forms of energy such as electricity and mechanical work. There is a need to regularly summarize the knowledge and research in the field of thermochemical energy storage in different parts of the world.

Development of a Database of Thermochemical Parameters for Use with the SOLGASMIX Computer Program

DTIC Science & Technology

1988-07-01

TITANIUM CHLORIDE (TICL4) CL4Wl(CR) TUNGSTEN CHLORIDE (WCL4) CL4Wl(G) TUNGSTEN CHLORIDE (WCL4) CL4ZR1(CR) ZIRCONIUM CHLORIDE ( ZRCL4 ) CL4ZR1(G) ZIRCONIUM...CHLORIDE ( ZRCL4 ) % % % CL5MO1(CR) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(CR,L) MOLYBDENUM CHLORIDE (MOCL5) CL5MO1(G) MOLYBDENUM CHLORIDE (MOCL5) CL5MOI(L

Parametric Study of Advanced Mixing of Fuel/Oxidant System in High Speed Gaseous Flows and Experimental Validation Planning

DTIC Science & Technology

2001-08-30

Body with Thermo-Chemical destribution of Heat-Protected System . In: Physical and Gasdynamic Phenomena in Supersonic Flows Over Bodies. Edit. By...Final Report on ISTC Contract # 1809p Parametric Study of Advanced Mixing of Fuel/Oxidant System in High Speed Gaseous Flows and Experimental...of Advanced Mixing of Fuel/Oxidant System in High Speed Gaseous Flows and Experimental Validation Planning 5c. PROGRAM ELEMENT NUMBER 5d. PROJECT

Validation of the Chemistry Module for the Euler Solver in Unified Flow Solver

DTIC Science & Technology

2012-03-01

traveling through the atmosphere there are three types of flow regimes that exist; the first is the continuum regime, second is the rarified regime and...The second method has been used in a program called Unified Flow Solver (UFS). UFS is currently being developed under collaborative efforts the Air...thermal non-equilibrium case and finally to a thermo-chemical non- equilibrium case. The data from the simulations will be compared to a second code

Process modeling for carbon-phenolic nozzle materials

NASA Technical Reports Server (NTRS)

Letson, Mischell A.; Bunker, Robert C.; Remus, Walter M., III; Clinton, R. G.

1989-01-01

A thermochemical model based on the SINDA heat transfer program is developed for carbon-phenolic nozzle material processes. The model can be used to optimize cure cycles and to predict material properties based on the types of materials and the process by which these materials are used to make nozzle components. Chemical kinetic constants for Fiberite MX4926 were determined so that optimization of cure cycles for the current Space Shuttle Solid Rocket Motor nozzle rings can be determined.

Testing of an advanced thermochemical conversion reactor system

NASA Astrophysics Data System (ADS)

1990-01-01

This report presents the results of work conducted by MTCI to verify and confirm experimentally the ability of the MTCI gasification process to effectively generate a high-quality, medium-Btu gas from a wider variety of feedstock and waste than that attainable in air-blown, direct gasification systems. The system's overall simplicity, due to the compact nature of the pulse combustor, and the high heat transfer rates attainable within the pulsating flow resonance tubes, provide a decided and near-term potential economic advantage for the MTCI indirect gasification system. The primary objective was the design, construction, and testing of a Process Design Verification System for an indirectly heated, thermochemical fluid-bed reactor and a pulse combustor an an integrated system that can process alternative renewable sources of energy such as biomass, black liquor, municipal solid waste and waste hydrocarbons, including heavy oils into a useful product gas. The test objectives for the biomass portion of this program were to establish definitive performance data on biomass feedstocks covering a wide range of feedstock qualities and characteristics. The test objectives for the black liquor portion of this program were to verify the operation of the indirect gasifier on commercial black liquor containing 65 percent solids at several temperature levels and to characterize the bed carbon content, bed solids particle size and sulfur distribution as a function of gasification conditions.

Carbonate thermochemical cycle for the production of hydrogen

DOEpatents

Collins, Jack L [Knoxville, TN; Dole, Leslie R [Knoxville, TN; Ferrada, Juan J [Knoxville, TN; Forsberg, Charles W [Oak Ridge, TN; Haire, Marvin J [Oak Ridge, TN; Hunt, Rodney D [Oak Ridge, TN; Lewis, Jr, Benjamin E [Knoxville, TN; Wymer, Raymond G [Oak Ridge, TN

2010-02-23

The present invention is directed to a thermochemical method for the production of hydrogen from water. The method includes reacting a multi-valent metal oxide, water and a carbonate to produce an alkali metal-multi-valent metal oxide compound, carbon dioxide, and hydrogen.

Bayesian Atmospheric Radiative Transfer (BART)Thermochemical Equilibrium Abundance (TEA) Code and Application to WASP-43b

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, Matthew O.; Cubillos, Patricio E.; Stemm, Madison; Foster, Andrew

2014-11-01

We present a new, open-source, Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. TEA uses the Gibbs-free-energy minimization method with an iterative Lagrangian optimization scheme. It initializes the radiative-transfer calculation in our Bayesian Atmospheric Radiative Transfer (BART) code. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. The code is tested against the original method developed by White at al. (1958), the analytic method developed by Burrows and Sharp (1999), and the Newton-Raphson method implemented in the open-source Chemical Equilibrium with Applications (CEA) code. TEA is written in Python and is available to the community via the open-source development site GitHub.com. We also present BART applied to eclipse depths of WASP-43b exoplanet, constraining atmospheric thermal and chemical parameters. This work was supported by NASA Planetary Atmospheres grant NNX12AI69G and NASA Astrophysics Data Analysis Program grant NNX13AF38G. JB holds a NASA Earth and Space Science Fellowship.

Mission analysis for the federal fuels from biomass program. Volume IV. Termochemical conversion of biomass to fuels and chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kohan, S.M.; Barkhordar, P.M.

1979-01-01

The thermochemical conversion of biomass feedstocks generally denotes technologies that use elevated temperatures to convert the fixed carbon content of biomass materials to produce other, more useful energy forms. Examples are combustion to produce heat, steam, electricity, or combinations of these; pyrolysis to produce gas (low- or intermediate-Btu), pyrolytic liquids and chemicals, and char; gasification to produce low or intermediate Btu gas (and, from IBG, additional products such as SNG, ammonia, methanol, or Fischer-Tropsch liquids); and liquefaction to produce heavy fuel oil or, with upgrading, lighter-boiling liquid products such as distillates, light fuel oils, or gasoline. This section discusses themore » selection of the feedstock used in the analysis of thermochemical conversion technologies. The following sections present detailed technical and economic evaluations of biomass conversion to electricity and steam by combustion, SNG by gasification and methanation, methanol by gasification and synthesis, oil by catalytic liquefaction, oil and char by pyrolysis, and ammonia by gasification and synthesis. The conversion options were reviewed with DOE for approval at the start of the project.« less

A finite element program for postbuckling calculations (PSTBKL)

NASA Technical Reports Server (NTRS)

Simitses, G. T.; Carlson, R. L.; Riff, R.

1991-01-01

The object of the research reported herein was to develop a general mathematical model and solution methodologies for analyzing the structural response of thin, metallic shell structures under large transient, cyclic, or static thermochemical loads. This report describes the computer program resulting from the research. Among the system responses associated with these loads and conditions are thermal buckling, creep buckling, and ratcheting. Thus geometric and material nonlinearities (of high order) have been anticipated and are considered in developing the mathematical model. The methodology is demonstrated through different problems of extension, shear, and of planar curved beams. Moreover, importance of the inclusion of large strains is clearly demonstrated, through the chosen applications.

SPE propulsion electrolyzer for NASA's integrated propulsion test article

NASA Technical Reports Server (NTRS)

1991-01-01

Hamilton Standard has delivered a 3000 PSI SPE Propulsion Electrolyzer Stack and Special Test Fixture to the NASA Lyndon B. Johnson Space Center (JSC) Integrated Propulsion Test Article (IPTA) program in June 1990, per contract NAS9-18030. This prototype unit demonstrates the feasibility of SPE-high pressure water electrolysis for future space applications such as Space Station propulsion and Lunar/Mars energy storage. The SPE-Propulsion Electrolyzer has met or exceeded all IPTA program goals. It continues to function as the primary hydrogen and oxygen source for the IPTA test bed at the NASA/JSC Propulsion and Power Division Thermochemical Test Branch.

Process development for elemental recovery from PGM tailings by thermochemical treatment: Preliminary major element extraction studies using ammonium sulphate as extracting agent.

PubMed

Mohamed, Sameera; van der Merwe, Elizabet M; Altermann, Wladyslaw; Doucet, Frédéric J

2016-04-01

Mine tailings can represent untapped secondary resources of non-ferrous, ferrous, precious, rare and trace metals. Continuous research is conducted to identify opportunities for the utilisation of these materials. This preliminary study investigated the possibility of extracting major elements from South African tailings associated with the mining of Platinum Group Metals (PGM) at the Two Rivers mine operations. These PGM tailings typically contain four major elements (11% Al2O3; 12% MgO; 22% Fe2O3; 34% Cr2O3), with lesser amounts of SiO2 (18%) and CaO (2%). Extraction was achieved via thermochemical treatment followed by aqueous dissolution, as an alternative to conventional hydrometallurgical processes. The thermochemical treatment step used ammonium sulphate, a widely available, low-cost, recyclable chemical agent. Quantification of the efficiency of the thermochemical process required the development and optimisation of the dissolution technique. Dissolution in water promoted the formation of secondary iron precipitates, which could be prevented by leaching thermochemically-treated tailings in 0.6M HNO3 solution. The best extraction efficiencies were achieved for aluminium (ca. 60%) and calcium (ca. 80%). 35% iron and 32% silicon were also extracted, alongside chromium (27%) and magnesium (25%). Thermochemical treatment using ammonium sulphate may therefore represent a promising technology for extracting valuable elements from PGM tailings, which could be subsequently converted to value-added products. However, it is not element-selective, and major elements were found to compete with the reagent to form water-soluble sulphate-metal species. Further development of this integrated process, which aims at achieving the full potential of utilisation of PGM tailings, is currently underway. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cost as a technology driver. [in aerospace R and D

NASA Technical Reports Server (NTRS)

Fitzgerald, P. E., Jr.; Savage, M.

1976-01-01

Cost managment as a guiding factor in optimum development of technology, and proper timing of cost-saving programs in the development of a system or technology with payoffs in development and operational advances are discussed and illustrated. Advances enhancing the performance of hardware or software advances raising productivity or reducing cost, are outlined, with examples drawn from: thermochemical thrust maximization, development of cryogenic storage tanks, improvements in fuel cells for Space Shuttle, design of a spacecraft pyrotechnic initiator, cost cutting by reduction in the number of parts to be joined, and cost cutting by dramatic reductions in circuit component number with small-scale double-diffused integrated circuitry. Program-focused supporting research and technology models are devised to aid judicious timing of cost-conscious research programs.

Intro to NREL's Thermochemical Pilot Plant

ScienceCinema

Magrini, Kim

2018-02-13

NREL's Thermochemical Pilot Plant converts biomass into higher hydrocarbon fuels and chemicals.NREL is researching biomass pyrolysis. The lab is examining how to upgrade bio-oils via stabilization. Along with this, NREL is developing the engineering system requirements for producing these fuels and chemicals at larger scales.

Turning manure into biochar through thermochemical conversion has the potential to become an exciting new way to handle waste

USDA-ARS?s Scientific Manuscript database

The livestock sector remains vigilant to address effective manure treatment that also safeguards natural resources. Livestock operations must balance business concerns, efficient energy management and environmental stewardship. Fortunately, thermochemical conversion technologies for converting lives...

Comprehensive characterisation of sewage sludge for thermochemical conversion processes - Based on Singapore survey.

PubMed

Chan, Wei Ping; Wang, Jing-Yuan

2016-08-01

Recently, sludge attracted great interest as a potential feedstock in thermochemical conversion processes. However, compositions and thermal degradation behaviours of sludge were highly complex and distinctive compared to other traditional feedstock led to a need of fundamental research on sludge. Comprehensive characterisation of sludge specifically for thermochemical conversion was carried out for all existing Water Reclamation Plants in Singapore. In total, 14 sludge samples collected based on the type, plant, and batch categorisation. Existing characterisation methods for physical and chemical properties were analysed and reviewed using the collected samples. Qualitative similarities and quantitative variations of different sludge samples were identified and discussed. Oxidation of inorganic in sludge during ash forming analysis found to be causing significant deviations on proximate and ultimate analysis. Therefore, alternative parameters and comparison basis including Fixed Residues (FR), Inorganic Matters (IM) and Total Inorganics (TI) were proposed for better understanding on the thermochemical characteristics of sludge. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hybrid Thermochemical/Biological Processing

NASA Astrophysics Data System (ADS)

Brown, Robert C.

The conventional view of biorefineries is that lignocellulosic plant material will be fractionated into cellulose, hemicellulose, lignin, and terpenes before these components are biochemically converted into market products. Occasionally, these plants include a thermochemical step at the end of the process to convert recalcitrant plant components or mixed waste streams into heat to meet thermal energy demands elsewhere in the facility. However, another possibility for converting high-fiber plant materials is to start by thermochemically processing it into a uniform intermediate product that can be biologically converted into a bio-based product. This alternative route to bio-based products is known as hybrid thermochemical/biological processing. There are two distinct approaches to hybrid processing: (a) gasification followed by fermentation of the resulting gaseous mixture of carbon monoxide (CO), hydrogen (H2), and carbon dioxide (CO2) and (b) fast pyrolysis followed by hydrolysis and/or fermentation of the anhydrosugars found in the resulting bio-oil. This article explores this "cart before the horse" approach to biorefineries.

The VLT LBG redshift survey - VI. Mapping H I in the proximity of z ˜ 3 LBGs with X-Shooter

NASA Astrophysics Data System (ADS)

Bielby, R. M.; Shanks, T.; Crighton, N. H. M.; Bornancini, C. G.; Infante, L.; Lambas, D. G.; Minniti, D.; Morris, S. L.; Tummuangpak, P.

2017-10-01

We present an analysis of the spatial distribution and dynamics of neutral hydrogen gas around galaxies using new X-Shooter observations of z ˜ 2.5-4 quasars. Adding the X-Shooter data to our existing data set of high-resolution quasar spectroscopy, we use a total sample of 29 quasars alongside ˜1700 Lyman Break Galaxies (LBGs) in the redshift range 2 ≲ z ≲ 3.5. We measure the Lyα forest auto-correlation function, finding a clustering length of s0 = 0.081 ± 0.006 h-1 Mpc, and the cross-correlation function with LBGs, finding a cross-clustering length of s0 = 0.27 ± 0.14 h-1 Mpc and power-law slope γ = 1.1 ± 0.2. Our results highlight the weakly clustered nature of neutral hydrogren systems in the Lyα forest. Building on this, we make a first analysis of the dependence of the clustering on absorber strength, finding a clear preference for stronger Lyα forest absorption features to be more strongly clustered around the galaxy population, suggesting that they trace on average higher mass haloes. Using the projected and 2-D cross-correlation functions, we constrain the dynamics of Lyα forest clouds around z ˜ 3 galaxies. We find a significant detection of large-scale infall of neutral hydrogen, with a constraint on the Lyα forest infall parameter of βF = 1.02 ± 0.22.

Analysis of thermo-chemical nonequilibrium models for carbon dioxide flows

NASA Technical Reports Server (NTRS)

Rock, Stacey G.; Candler, Graham V.; Hornung, Hans G.

1992-01-01

The aerothermodynamics of thermochemical nonequilibrium carbon dioxide flows is studied. The chemical kinetics models of McKenzie and Park are implemented in separate three-dimensional computational fluid dynamics codes. The codes incorporate a five-species gas model characterized by a translational-rotational and a vibrational temperature. Solutions are obtained for flow over finite length elliptical and circular cylinders. The computed flowfields are then employed to calculate Mach-Zehnder interferograms for comparison with experimental data. The accuracy of the chemical kinetics models is determined through this comparison. Also, the methodology of the three-dimensional thermochemical nonequilibrium code is verified by the reproduction of the experiments.

Thermochemical conversion of waste tyres-a review.

PubMed

Labaki, Madona; Jeguirim, Mejdi

2017-04-01

A review of the energy recovery from waste tyres is presented and focuses on the three thermochemical processes used to valorise waste tyres: pyrolysis, gasification, and combustion/incineration. After recalling the chemical composition of tyres, the thermogravimetric behaviours of tyres or their components under different atmospheres are described. Different kinetic studies on the thermochemical processes are treated. Then, the three processes were investigated, with a particular attention given to the gasification, due to the information unavailability on this process. Pyrolysis is a thermochemical conversion to produce a hydrocarbon rich gas mixture, condensable liquids or tars, and a carbon-rich solid residue. Gasification is a form of pyrolysis, carried out at higher temperatures and under given atmosphere (air, steam, oxygen, carbon dioxide, etc.) in order to yield mainly low molecular weight gaseous products. Combustion is a process that needs a fuel and an oxidizer with an ignition system to produce heat and/or steam. The effects of various process parameters such as temperature, heating rate, residence time, catalyst addition, etc. on the energy efficiency and the products yields and characteristics are mainly reviewed. These thermochemical processes are considered to be the more attractive and practicable methods for recovering energy and material from waste tyres. For the future, they are the main promising issue to treat and valorise used tyres. However, efforts should be done in developing more efficient technical systems.

On the thermo-chemical origin of the stratified region at the top of the Earth's core

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi

2018-03-01

I developed a combined model of the thermal and chemical evolution of the Earth's core and investigated its influence on a thermochemically stable region beneath the core-mantle boundary (CMB). The chemical effects of the growing stable region are caused by the equilibrium chemical reaction between silicate and the metallic core. The thermal effects can be characterized by the growth of the sub-isentropic shell, which may have a rapid growth rate compared to that of the chemically stable region. When the present-day CMB heat flow was varied, the origin of the stable region changed from chemical to thermochemical to purely thermal because the rapid growth of the sub-isentropic shell can replace the chemically stable region. Physically reasonable values of the present-day CMB heat flow that can maintain the geodynamo action over 4 billion years should be between 8 and 11 TW. To constrain the thickness of the thermochemically stable region beneath the CMB, the chemical diffusivity is important and should be ∼O(10-8) m2/s to obtain a thickness of the thermochemically stable region beneath the CMB consistent with that inferred from geomagnetic secular variations (140 km). However, the strength of the stable region found in this study is too high to be consistent with the constraint on the stability of the stable region inferred from geomagnetic secular variations.

Innovative solar thermochemical water splitting.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.

2008-02-01

Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximitymore » and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.« less

Biomass for thermochemical conversion: targets and challenges

PubMed Central

Tanger, Paul; Field, John L.; Jahn, Courtney E.; DeFoort, Morgan W.; Leach, Jan E.

2013-01-01

Bioenergy will be one component of a suite of alternatives to fossil fuels. Effective conversion of biomass to energy will require the careful pairing of advanced conversion technologies with biomass feedstocks optimized for the purpose. Lignocellulosic biomass can be converted to useful energy products via two distinct pathways: enzymatic or thermochemical conversion. The thermochemical pathways are reviewed and potential biotechnology or breeding targets to improve feedstocks for pyrolysis, gasification, and combustion are identified. Biomass traits influencing the effectiveness of the thermochemical process (cell wall composition, mineral and moisture content) differ from those important for enzymatic conversion and so properties are discussed in the language of biologists (biochemical analysis) as well as that of engineers (proximate and ultimate analysis). We discuss the genetic control, potential environmental influence, and consequences of modification of these traits. Improving feedstocks for thermochemical conversion can be accomplished by the optimization of lignin levels, and the reduction of ash and moisture content. We suggest that ultimate analysis and associated properties such as H:C, O:C, and heating value might be more amenable than traditional biochemical analysis to the high-throughput necessary for the phenotyping of large plant populations. Expanding our knowledge of these biomass traits will play a critical role in the utilization of biomass for energy production globally, and add to our understanding of how plants tailor their composition with their environment. PMID:23847629

Thermal Storage Applications Workshop. Volume 1: Plenary Session Analysis

NASA Technical Reports Server (NTRS)

1979-01-01

The importance of the development of inexpensive and efficient thermal and thermochemical energy storage technology to the solar power program is discussed in a summary of workship discussions held to exchange information and plan for future systems. Topics covered include storage in central power applications such as the 10 MW-e demonstration pilot receiver to be constructed in Barstow, California; storage for small dispersed systems, and problems associated with the development of storage systems for solar power plants interfacing with utility systems.

The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting

DOE PAGES

Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia; ...

2018-01-01

We report the discovery of a new class of oxides – poly-cation oxides (PCOs) – that consist of multiple cations and can thermochemically split water in a two-step cycle to produce hydrogen (H 2 ) and oxygen (O 2 ).

Program and charts for determining shock tube, and expansion tunnel flow quantities for real air

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1975-01-01

A computer program in FORTRAN 4 language was written to determine shock tube, expansion tube, and expansion tunnel flow quantities for real-air test gas. This program permits, as input data, a number of possible combinations of flow quantities generally measured during a test. The versatility of the program is enhanced by the inclusion of such effects as a standing or totally reflected shock at the secondary diaphragm, thermochemical-equilibrium flow expansion and frozen flow expansion for the expansion tube and expansion tunnel, attenuation of the flow in traversing the acceleration section of the expansion tube, real air as the acceleration gas, and the effect of wall boundary layer on the acceleration section air flow. Charts which provide a rapid estimation of expansion tube performance prior to a test are included.

Neutralization and Acid Dissociation of Hydrogen Carbonate Ion: A Thermochemical Approach

ERIC Educational Resources Information Center

Koga, Nobuyoshi; Shigedomi, Kana; Kimura, Tomoyasu; Tatsuoka, Tomoyuki; Mishima, Saki

2013-01-01

A laboratory inquiry into the thermochemical relationships in the reaction between aqueous solutions of NaHCO[subscript 3] and NaOH is described. The enthalpy change for this reaction, delta[subscript r]H, and that for neutralization of strong acid and NaOH(aq), delta[subscript n]H, are determined calorimetrically; the explanation for the…

Thermochemical properties of flame gases from fine wildland fuels

Treesearch

Frank A. Albini

1979-01-01

Describes a theoretical model for calculating thermochemical properties of the gaseous fuel that burns in the free flame at the edge of a spreading fire in fine forest fuels. Predicted properties are the heat of combustion, stoichiometric air/fuel mass ratio, mass-averaged temperature, and mass fraction of unburned fuel in the gas mixture emitted from the flame-...

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1992-01-01

Presented is a collection of papers on research activities carried out during the funding period of October 1991 to March 1992. Topics covered include: blunt body flows in thermochemical equilibrium; thermochemical relaxation in high enthalpy nozzle flow; single expansion ramp nozzle simulations; lunar return aerobraking; line boundary problem for three dimensional grids; and unsteady shock induced combustion.

Torrefaction? What’s that?

Treesearch

D. Mitchell; T. Elder

2010-01-01

Torrefaction is a thermo-chemical process that reduces the moisture content of wood and transforms it into a brittle, char-type material. The thermo-chemical process can reduce the mass of wood by 20-30% resulting in a denser, higher-valued product that can be transported more economically than traditional wood chips. Through torrefaction, wood may retain 90% of the...

Development of a practical photochemical energy storage system. Quarterly report. [Interconversion between norbornadiene and quadricyclene for thermochemical heat storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hautala, R.R.; Kutal, C.R.

1977-06-15

Research on polymeric organic sensitizers and polymeric inorganic sensitizers for the conversion of norbornadine to quadricyclene and catalysts for the conversion of quadricyclene to norbornadine is described. The interconversion of norbornadine and quadricyclene is studied for its possible use for thermochemical solar energy storage. (WHK)

Modeling of Laser Vaporization and Plume Chemistry in a Boron Nitride Nanotube Production Rig

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Fay, Catharine C.

2012-01-01

Flow in a pressurized, vapor condensation (PVC) boron nitride nanotube (BNNT) production rig is modeled. A laser provides a thermal energy source to the tip of a boron ber bundle in a high pressure nitrogen chamber causing a plume of boron-rich gas to rise. The buoyancy driven flow is modeled as a mixture of thermally perfect gases (B, B2, N, N2, BN) in either thermochemical equilibrium or chemical nonequilibrium assuming steady-state melt and vaporization from a 1 mm radius spot at the axis of an axisymmetric chamber. The simulation is intended to define the macroscopic thermochemical environment from which boron-rich species, including nanotubes, condense out of the plume. Simulations indicate a high temperature environment (T > 4400K) for elevated pressures within 1 mm of the surface sufficient to dissociate molecular nitrogen and form BN at the base of the plume. Modifications to Program LAURA, a finite-volume based solver for hypersonic flows including coupled radiation and ablation, are described to enable this simulation. Simulations indicate that high pressure synthesis conditions enable formation of BN vapor in the plume that may serve to enhance formation of exceptionally long nanotubes in the PVC process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, J.; Moon, T.J.; Howell, J.R.

This paper presents an analysis of the heat transfer occurring during an in-situ curing process for which infrared energy is provided on the surface of polymer composite during winding. The material system is Hercules prepreg AS4/3501-6. Thermoset composites have an exothermic chemical reaction during the curing process. An Eulerian thermochemical model is developed for the heat transfer analysis of helical winding. The model incorporates heat generation due to the chemical reaction. Several assumptions are made leading to a two-dimensional, thermochemical model. For simplicity, 360{degree} heating around the mandrel is considered. In order to generate the appropriate process windows, the developedmore » heat transfer model is combined with a simple winding time model. The process windows allow for a proper selection of process variables such as infrared energy input and winding velocity to give a desired end-product state. Steady-state temperatures are found for each combination of the process variables. A regression analysis is carried out to relate the process variables to the resulting steady-state temperatures. Using regression equations, process windows for a wide range of cylinder diameters are found. A general procedure to find process windows for Hercules AS4/3501-6 prepreg tape is coded in a FORTRAN program.« less

Thermodynamic properties of minerals

USGS Publications Warehouse

Robie, Richard A.

1962-01-01

In the ten years since the publication of the national Bureau of Standards comprehensive tables of thermochemical properties, by Rossini and other (1952), a very large body of modern calorimetric and equilibrium data has become available. Because of the complex interrelations among many thermochemical data and the necessity for internal consistency among these values, a complete revision of this standard reference is required. This is also true of the summaries of thermochemical data for the sulfides (Richardson and Jeffes 1952) and for the oxides (Coughlin 1954). The following tables present critically selected values for the heat and free energy of formation, the logarithm of the equilibrium constant of formation Log Kf, the entropy and the molar volume, at 298.15°K (25.0°C) and one atmosphere for minerals.

Quantitative Thermochemical Measurements in High-Pressure Gaseous Combustion

NASA Technical Reports Server (NTRS)

Kojima, Jun J.; Fischer, David G.

2012-01-01

We present our strategic experiment and thermochemical analyses on combustion flow using a subframe burst gating (SBG) Raman spectroscopy. This unconventional laser diagnostic technique has promising ability to enhance accuracy of the quantitative scalar measurements in a point-wise single-shot fashion. In the presentation, we briefly describe an experimental methodology that generates transferable calibration standard for the routine implementation of the diagnostics in hydrocarbon flames. The diagnostic technology was applied to simultaneous measurements of temperature and chemical species in a swirl-stabilized turbulent flame with gaseous methane fuel at elevated pressure (17 atm). Statistical analyses of the space-/time-resolved thermochemical data provide insights into the nature of the mixing process and it impact on the subsequent combustion process in the model combustor.

Analysis of volatile combustion products and a study of their toxicological effects.

NASA Technical Reports Server (NTRS)

Seader, J. D.; Einhorn, I. N.; Drake, W. O.; Mihlfeith, C. M.

1972-01-01

An experimental program was conducted to study the thermochemical, flammability and toxicological characteristics of uncoated and coated polyisocyanurate foams. The coatings used were fluorinated copolymer and an intumescent material. Combustion and pyrolysis gases were analyzed by gas chromatography and mass spectrometry. The LD-50 and LD-100 tests were performed on Sprague-Dawley rats housed in an environmental chamber. The isocyanurate foam, fluorinated-copolymer-coated foam, and the intumescent-coated foam were found to have excellent flammability and insulation characteristics, although smoke development was substantial.

Numerical Simulation of Fluid Dynamics and Payload Dissemination in a Dual-Chamber Grenade

DTIC Science & Technology

1993-02-01

dependence obtained from tabulated data ( Stull and Prophet 1971). c,,/* = A1 + A 2T + A3T2 + A4T3 + A 5 TV (8) where the mixture specific heat is given by...Hill, NY, 1979. Stull , D.R., and Prophet, H., "JANNAF Thermochemical Tables," 2nd ed., National Bureau of Standards, NSRDS-Rept. 37, June 1971. Turetsky...AL 36360 Radford, VA 24141-0298 Program Manager U.S. Tank-Automotive Command ATTN: AMCPM-ABMS, T. Dean Warren, MI 48092-2498 27 No. of No. of Commander

High-Resolution Photoionization, Photoelectron and Photodissociation Studies. Determination of Accurate Energetic and Spectroscopic Database for Combustion Radicals and Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ng, Cheuk-Yiu

2016-04-25

The main goal of this research program was to obtain accurate thermochemical and spectroscopic data, such as ionization energies (IEs), 0 K bond dissociation energies, 0 K heats of formation, and spectroscopic constants for radicals and molecules and their ions of relevance to combustion chemistry. Two unique, generally applicable vacuum ultraviolet (VUV) laser photoion-photoelectron apparatuses have been developed in our group, which have used for high-resolution photoionization, photoelectron, and photodissociation studies for many small molecules of combustion relevance.

Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

ERIC Educational Resources Information Center

Cigdemoglu, Ceyhan; Geban, Omer

2015-01-01

The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, Carlos E.

1980-01-01

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Cascading pressure reactor and method for solar-thermochemical reactions

DOEpatents

Ermanoski, Ivan

2017-11-14

Reactors and methods for solar thermochemical reactions are disclosed. The reactors and methods include a cascade of reduction chambers at successively lower pressures that leads to over an order of magnitude pressure decrease compared to a single-chambered design. The resulting efficiency gains are substantial, and represent an important step toward practical and efficient solar fuel production on a large scale.

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

DOEpatents

Bamberger, C.E.

A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass

Treesearch

Zhaojiang Wang; Menghua Qin; J.Y. Zhu; Guoyu Tian; Zongquan Li

2013-01-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical–biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by...

Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

ERIC Educational Resources Information Center

Journal of Chemical Education, 2015

2015-01-01

This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.

Thermochemical recovery of heat contained in flue gases by means of bioethanol conversion

NASA Astrophysics Data System (ADS)

Pashchenko, D. I.

2013-06-01

In the present paper consideration is being given to the use of bioethanol in the schemes of thermochemical recovery of heat contained in exit flue gases. Schematic diagrams illustrate the realization of thermochemical heat recovery by implementing ethanol steam conversion and conversion of ethanol by means of products of its complete combustion. The feasibility of attaining a high degree of recovery of heat contained in flue gases at the moderate temperature (up to 450°C) of combustion components is demonstrated in the example of the energy balance of the system for thermochemical heat recovery. The simplified thermodynamic analysis of the process of ethanol steam conversion was carried out in order to determine possible ranges of variation of process variables (temperature, pressure, composition) of a reaction mixture providing the efficient heat utilization. It was found that at the temperature above 600 K the degree of ethanol conversion is near unity. The equilibrium composition of products of reaction of ethanol steam conversion has been identified for different temperatures at which the process occurs at the ratio H2O/EtOH = 1 and at the pressure of 0.1 MPa. The obtained results of calculation agree well with the experimental data.

Optimized structure and thermochemical properties of flavonoids determined by the CHIH(medium) DFT model chemistry versus experimental techniques

NASA Astrophysics Data System (ADS)

Mendoza-Wilson, Ana María.; Lardizabal-Gutiérrez, Daniel; Torres-Moye, Enrique; Fuentes-Cobas, Luis; Balandrán-Quintana, René R.; Camacho-Dávila, Alejandro; Quintero-Ramos, Armando; Glossman-Mitnik, Daniel

2007-12-01

The purpose of this work was to evaluate the accuracy of the CHIH(medium)-DFT model chemistry (PBEg/CBSB2 ∗∗//PBEg/CBSB4) in the determination of the optimized structure and thermochemical properties of heterocyclic systems of medium size such as flavonoids, wherefore were selected three of the most abundant flavonoids in vegetable tissues, and which posses the higher antioxidant activity: quercetin, (+)-catechin and cyanidin. As reference systems were employed three cyclic compounds: phenol, catechol and resorcinol. The thermochemical properties evaluated were enthalpy of formation, bond dissociation enthalpy (BDE) and ionization potential (IP), following the scheme of isodesmic reactions. The theoretical results were compared with experimental data generated by X-ray diffraction and calorimetric techniques realized in part by us, whereas other data were taken from the literature. The results obtained in this work reveal that the CHIH(medium)-DFT model chemistry represents an accurate computational tool to calculate structural and thermochemical properties in the studied flavonoid and reference compounds. The average absolute deviation of enthalpy of formation for reference compounds was 3.0 kcal/mol, 2.64 kcal/mol for BDE, and 2.97 kcal/mol for IP.

Evaluation of the performance of MP4-based procedures for a wide range of thermochemical and kinetic properties

NASA Astrophysics Data System (ADS)

Yu, Li-Juan; Wan, Wenchao; Karton, Amir

2016-11-01

We evaluate the performance of standard and modified MPn procedures for a wide set of thermochemical and kinetic properties, including atomization energies, structural isomerization energies, conformational energies, and reaction barrier heights. The reference data are obtained at the CCSD(T)/CBS level by means of the Wn thermochemical protocols. We find that none of the MPn-based procedures show acceptable performance for the challenging W4-11 and BH76 databases. For the other thermochemical/kinetic databases, the MP2.5 and MP3.5 procedures provide the most attractive accuracy-to-computational cost ratios. The MP2.5 procedure results in a weighted-total-root-mean-square deviation (WTRMSD) of 3.4 kJ/mol, whilst the computationally more expensive MP3.5 procedure results in a WTRMSD of 1.9 kJ/mol (the same WTRMSD obtained for the CCSD(T) method in conjunction with a triple-zeta basis set). We also assess the performance of the computationally economical CCSD(T)/CBS(MP2) method, which provides the best overall performance for all the considered databases, including W4-11 and BH76.

Numeric Databases in Chemical Thermodynamics at the National Institute of Standards and Technology

PubMed Central

Chase, Malcolm W.

1989-01-01

During the past year the activities of the Chemical Thermodynamics Data Center and the JANAF Thermochemical Tables project have been combined to obtain an extensive collection of thermodynamic information for many chemical species, including the elements. Currently available are extensive bibliographic collections and data files of heat capacity, enthalpy, vapor pressure, phase transitions, etc. Future plans related to materials science are to improve the metallic oxide temperature dependent tabulations, upgrade the recommended values periodically, and maintain the bibliographic citations and the thermochemical data current. The recommended thermochemical information is maintained on-line, and tied to the calculational routines within the data center. Recent thermodynamic evaluations on the elements and oxides will be discussed, as well as studies in related activities at NIST. PMID:28053395

Estimates of thermochemical relaxation lengths behind normal shock waves relevant to manned lunar and Mars return missions, the aeroassist flight experiment, and Mars entry

NASA Technical Reports Server (NTRS)

Howe, John T.

1991-01-01

Thermochemical relaxation distances behind the strong normal shock waves associated with vehicles that enter the Earth atmosphere upon returning from a manned lunar or Mars mission are estimated. The relaxation distances for a Mars entry are estimated as well, in order to highlight the extent of the relaxation phenomena early in currently envisioned space exploration studies. The thermochemical relaxation length for the Aeroassist Flight Experiment is also considered. These estimates provide an indication as to whether finite relaxation needs to be considered in subsequent detailed analyses. For the Mars entry, relaxation phenomena that are fully coupled to the flow field equations are used. The relaxation-distance estimates can be scaled to flight conditions other than those discussed.

Thermal barrier coating life prediction model

NASA Technical Reports Server (NTRS)

Pilsner, B. H.; Hillery, R. V.; Mcknight, R. L.; Cook, T. S.; Kim, K. S.; Duderstadt, E. C.

1986-01-01

The objectives of this program are to determine the predominant modes of degradation of a plasma sprayed thermal barrier coating system, and then to develop and verify life prediction models accounting for these degradation modes. The program is divided into two phases, each consisting of several tasks. The work in Phase 1 is aimed at identifying the relative importance of the various failure modes, and developing and verifying life prediction model(s) for the predominant model for a thermal barrier coating system. Two possible predominant failure mechanisms being evaluated are bond coat oxidation and bond coat creep. The work in Phase 2 will develop design-capable, causal, life prediction models for thermomechanical and thermochemical failure modes, and for the exceptional conditions of foreign object damage and erosion.

Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

NASA Technical Reports Server (NTRS)

Ota, K.; Conger, W. L.

1977-01-01

The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

The African and Pacific Superplumes and Thermochemical Piles and Their Relationship to Supercontinent Pangea

NASA Astrophysics Data System (ADS)

Zhong, S.; Leng, W.; Zhang, N.; McNamara, A. K.

2008-12-01

The long-wavelength structure for the present-day Earth's mantle is characterized by circum-Pacific subduction and the antipodal African and Pacific superplumes. The African and Pacific superplumes are anchored on two major thermochemical piles that extend from the core-mantle boundary (CMB) to possibly >500 km above CMB. These two superplumes are where most of large igneous provinces (LIPs) and plume-related volcanism are originated in the last 250 Ma. The thermochemical piles may provide distinct geochemical signatures observed in oceanic island basalts, although it remains controversial whether the piles consist of primordial mantle materials or recycled crust and lithosphere. Geodynamic modeling has demonstrated that the main structural features of the mantle including the circum-Pacific subduction, African and Pacific superplumes, and the thermochemical piles, are closely related to mantle convection associated with plate motion history for the last 120 Ma. However, outstanding questions remain. When did the African and Pacific superplumes and thermochemical piles start to take the current forms? How stable and stationary have they been in the mantle? How are they related to the observations of tectonics and volcanism priori to 120 Ma ago? Our recent studies on long-wavelength mantle convection and supercontinent cycles suggest that the African and Pacific superplumes and thermochemical piles are dynamic features and that they may move laterally in response to mantle flow associated with surface plate motion, such as past subduction and convergence between Laurentia and Gondwana. In particular, our studies suggest that the African superplume and pile did not form until Laurentia and Gondwana collided to form Pangea, while the Pacific anomaly may have been there for a longer time. Our results also suggest that, after lengthy convergence between Laurentia and Gondwana that pushed away the pile materials away from the African hemisphere, later subduction surrounding Pangea may not bring enough chemically dense mantle materials to form the African pile, if the pile consists of the primordial mantle, thus suggesting an origin of the recycled crust and lithosphere for the pile. While focusing on the African anomaly, we will also discuss potential ways to constrain the evolution of the Pacific superplume and pile.

Analysis of medium-BTU gasification condensates, June 1985-June 1986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, D.C.

1987-05-01

This report provides the final results of chemical and physical analysis of condensates from biomass gasification systems which are part of the US Department of Energy Biomass Thermochemical Conversion Program. The work described in detail in this report involves extensive analysis of condensates from four medium-BTU gasifiers. The analyses include elemental analysis, ash, moisture, heating value, density, specific chemical analysis, ash, moisture, heating value, density, specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, Carbon-13 nuclear magnetic resonance spectrometry) and Ames Assay. This work was an extension of a broader study earlier completed of the condensates of all the gasifers andmore » pyrolyzers in the Biomass Thermochemical Conversion Program. The analytical data demonstrates the wide range of chemical composition of the organics recoverd in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures as a result of formation of polycyclic aromatic hydrocarbons in high concentrations. Future studies of the time/temperature relationship to tar composition and the effect of processing atmosphere should be undertaken. Further processing of the condensates either as wastewater treatment or upgrading of the organics to useful products is also recommended. 15 refs., 4 figs., 4 tabs.« less

Comparative life cycle assessment of lignocellulosic ethanol production: biochemical versus thermochemical conversion.

PubMed

Mu, Dongyan; Seager, Thomas; Rao, P Suresh; Zhao, Fu

2010-10-01

Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle assessment model that facilitates effective decision-making regarding lignocellulosic ethanol production.

Definitive Ideal-Gas Thermochemical Functions of the H216O Molecule

NASA Astrophysics Data System (ADS)

Furtenbacher, Tibor; Szidarovszky, Tamás; Hrubý, Jan; Kyuberis, Aleksandra A.; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Császár, Attila G.

2016-12-01

A much improved temperature-dependent ideal-gas internal partition function, Qint(T), of the H216O molecule is reported for temperatures between 0 and 6000 K. Determination of Qint(T) is principally based on the direct summation technique involving all accurate experimental energy levels known for H216O (almost 20 000 rovibrational energies including an almost complete list up to a relative energy of 7500 cm-1), augmented with a less accurate but complete list of first-principles computed rovibrational energy levels up to the first dissociation limit, about 41 000 cm-1 (the latter list includes close to one million bound rovibrational energy levels up to J = 69, where J is the rotational quantum number). Partition functions are developed for ortho- and para-H216O as well as for their equilibrium mixture. Unbound rovibrational states of H216O above the first dissociation limit are considered using an approximate model treatment. The effect of the excited electronic states on the thermochemical functions is neglected, as their contribution to the thermochemical functions is negligible even at the highest temperatures considered. Based on the high-accuracy Qint(T) and its first two moments, definitive results, in 1 K increments, are obtained for the following thermochemical functions: Gibbs energy, enthalpy, entropy, and isobaric heat capacity. Reliable uncertainties (approximately two standard deviations) are estimated as a function of temperature for each quantity determined. These uncertainties emphasize that the present results are the most accurate ideal-gas thermochemical functions ever produced for H216O. It is recommended that the new value determined for the standard molar enthalpy increment at 298.15 K, 9.904 04 ± 0.000 01 kJ mol-1, should replace the old CODATA datum, 9.905 ± 0.005 kJ mol-1.

Comparative Life Cycle Assessment of Lignocellulosic Ethanol Production: Biochemical Versus Thermochemical Conversion

NASA Astrophysics Data System (ADS)

Mu, Dongyan; Seager, Thomas; Rao, P. Suresh; Zhao, Fu

2010-10-01

Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle assessment model that facilitates effective decision-making regarding lignocellulosic ethanol production.

In vivo comparison of simultaneous versus sequential injection technique for thermochemical ablation in a porcine model.

PubMed

Cressman, Erik N K; Shenoi, Mithun M; Edelman, Theresa L; Geeslin, Matthew G; Hennings, Leah J; Zhang, Yan; Iaizzo, Paul A; Bischof, John C

2012-01-01

To investigate simultaneous and sequential injection thermochemical ablation in a porcine model, and compare them to sham and acid-only ablation. This IACUC-approved study involved 11 pigs in an acute setting. Ultrasound was used to guide placement of a thermocouple probe and coaxial device designed for thermochemical ablation. Solutions of 10 M acetic acid and NaOH were used in the study. Four injections per pig were performed in identical order at a total rate of 4 mL/min: saline sham, simultaneous, sequential, and acid only. Volume and sphericity of zones of coagulation were measured. Fixed specimens were examined by H&E stain. Average coagulation volumes were 11.2 mL (simultaneous), 19.0 mL (sequential) and 4.4 mL (acid). The highest temperature, 81.3°C, was obtained with simultaneous injection. Average temperatures were 61.1°C (simultaneous), 47.7°C (sequential) and 39.5°C (acid only). Sphericity coefficients (0.83-0.89) had no statistically significant difference among conditions. Thermochemical ablation produced substantial volumes of coagulated tissues relative to the amounts of reagents injected, considerably greater than acid alone in either technique employed. The largest volumes were obtained with sequential injection, yet this came at a price in one case of cardiac arrest. Simultaneous injection yielded the highest recorded temperatures and may be tolerated as well as or better than acid injection alone. Although this pilot study did not show a clear advantage for either sequential or simultaneous methods, the results indicate that thermochemical ablation is attractive for further investigation with regard to both safety and efficacy.

a Protocol for High-Accuracy Theoretical Thermochemistry

NASA Astrophysics Data System (ADS)

Welch, Bradley; Dawes, Richard

2017-06-01

Theoretical studies of spectroscopy and reaction dynamics including the necessary development of potential energy surfaces rely on accurate thermochemical information. The Active Thermochemical Tables (ATcT) approach by Ruscic^{1} incorporates data for a large number of chemical species from a variety of sources (both experimental and theoretical) and derives a self-consistent network capable of making extremely accurate estimates of quantities such as temperature dependent enthalpies of formation. The network provides rigorous uncertainties, and since the values don't rely on a single measurement or calculation, the provenance of each quantity is also obtained. To expand and improve the network it is desirable to have a reliable protocol such as the HEAT approach^{2} for calculating accurate theoretical data. Here we present and benchmark an approach based on explicitly-correlated coupled-cluster theory and vibrational perturbation theory (VPT2). Methyldioxy and Methyl Hydroperoxide are important and well-characterized species in combustion processes and begin the family of (ethyl-, propyl-based, etc) similar compounds (much less is known about the larger members). Accurate anharmonic frequencies are essential to accurately describe even the 0 K enthalpies of formation, but are especially important for finite temperature studies. Here we benchmark the spectroscopic and thermochemical accuracy of the approach, comparing with available data for the smallest systems, and comment on the outlook for larger systems that are less well-known and characterized. ^{1}B. Ruscic, Active Thermochemical Tables (ATcT) values based on ver. 1.118 of the Thermochemical Network (2015); available at ATcT.anl.gov ^{2}A. Tajti, P. G. Szalay, A. G. Császár, M. Kállay, J. Gauss, E. F. Valeev, B. A. Flowers, J. Vázquez, and J. F. Stanton. JCP 121, (2004): 11599.

Methodology Report for H2SModel

DTIC Science & Technology

2012-01-01

thermochemical) cal (thermochemical/ cm2) curie degree (angl e ) degree Fahrenheit electron volt erg erg/second foot foot- pound- force gal l... Dosimetry ) model developed by Asgharian ([7, 10]) . First, transport of H2S in the lung is modeled by the area-averaged convective-diffusion equation...performance. Technical Report DNA TR 85 52, Defense Nuclear Agency, Washington, D.C. , 1984. [10] Asgharian, B., et al. Multiple Path Particle Dosimetry

A comparison of producer gas, biochar, and activated carbon from two distributed scale thermochemical conversion systems used to process forest biomass

Treesearch

Nathaniel Anderson; J. Greg Jones; Deborah Page-Dumroese; Daniel McCollum; Stephen Baker; Daniel Loeffler; Woodam Chung

2013-01-01

Thermochemical biomass conversion systems have the potential to produce heat, power, fuels and other products from forest biomass at distributed scales that meet the needs of some forest industry facilities. However, many of these systems have not been deployed in this sector and the products they produce from forest biomass have not been adequately described or...

Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

NASA Technical Reports Server (NTRS)

Milam, Stefanie N.; Charnley, Steven B.

2011-01-01

We will present observations of phosphorus-bearing species in circumstellar envelopes, including carbon- and oxygen-rich shells 1. New models of thermochemical equilibrium chemistry have been developed to interpret, and constrained by these data. These calculations will also be presented and compared to the numerous P-bearing species already observed in evolved stars. Predictions for other viable species will be made for observations with Herschel and ALMA.

Computational Chemistry Comparison and Benchmark Database

National Institute of Standards and Technology Data Gateway

SRD 101 NIST Computational Chemistry Comparison and Benchmark Database (Web, free access)   The NIST Computational Chemistry Comparison and Benchmark Database is a collection of experimental and ab initio thermochemical properties for a selected set of molecules. The goals are to provide a benchmark set of molecules for the evaluation of ab initio computational methods and allow the comparison between different ab initio computational methods for the prediction of thermochemical properties.

Linking lowermost mantle structure, core-mantle boundary heat flux and mantle plume formation

NASA Astrophysics Data System (ADS)

Li, Mingming; Zhong, Shijie; Olson, Peter

2018-04-01

The dynamics of Earth's lowermost mantle exert significant control on the formation of mantle plumes and the core-mantle boundary (CMB) heat flux. However, it is not clear if and how the variation of CMB heat flux and mantle plume activity are related. Here, we perform geodynamic model experiments that show how temporal variations in CMB heat flux and pulses of mantle plumes are related to morphologic changes of the thermochemical piles of large-scale compositional heterogeneities in Earth's lowermost mantle, represented by the large low shear velocity provinces (LLSVPs). We find good correlation between the morphologic changes of the thermochemical piles and the time variation of CMB heat flux. The morphology of the thermochemical piles is significantly altered during the initiation and ascent of strong mantle plumes, and the changes in pile morphology cause variations in the local and the total CMB heat flux. Our modeling results indicate that plume-induced episodic variations of CMB heat flux link geomagnetic superchrons to pulses of surface volcanism, although the relative timing of these two phenomena remains problematic. We also find that the density distribution in thermochemical piles is heterogeneous, and that the piles are denser on average than the surrounding mantle when both thermal and chemical effects are included.

Lignin structural alterations in thermochemical pretreatments with limited delignification

DOE PAGES

Pu, Yunqiao; Hu, Fan; Huang, Fang; ...

2015-08-02

Lignocellulosic biomass has a complex and rigid cell wall structure that makes biomass recalcitrant to biological and chemical degradation. Among the three major structural biopolymers (i.e., cellulose, hemicellulose and lignin) in plant cell walls, lignin is considered the most recalcitrant component and generally plays a negative role in the biochemical conversion of biomass to biofuels. The conversion of biomass to biofuels through a biochemical platform usually requires a pretreatment stage to reduce the recalcitrance. Pretreatment renders compositional and structural changes of biomass with these changes ultimately govern the efficiency of the subsequent enzymatic hydrolysis. Dilute acid, hot water, steam explosion,more » and ammonia fiber expansion pretreatments are among the leading thermochemical pretreatments with a limited delignification that can reduce biomass recalcitrance. Practical applications of these pretreatment are rapidly developing as illustrated by recent commercial scale cellulosic ethanol plants. While these thermochemical pretreatments generally lead to only a limited delignification and no significant change of lignin content in the pretreated biomass, the lignin transformations that occur during these pretreatments and the roles they play in recalcitrance reduction is an important research aspect. This review highlights recent advances in our understanding of lignin alterations during these limited delignification thermochemical pretreatments, with emphasis on lignin chemical structures, molecular weights, and redistributions in the pretreated biomass.« less

Water Footprint and Land Requirement of Solar Thermochemical Jet-Fuel Production.

PubMed

Falter, Christoph; Pitz-Paal, Robert

2017-11-07

The production of alternative fuels via the solar thermochemical pathway has the potential to provide supply security and to significantly reduce greenhouse gas emissions. H 2 O and CO 2 are converted to liquid hydrocarbon fuels using concentrated solar energy mediated by redox reactions of a metal oxide. Because attractive production locations are in arid regions, the water footprint and the land requirement of this fuel production pathway are analyzed. The water footprint consists of 7.4 liters per liter of jet fuel of direct demand on-site and 42.4 liters per liter of jet fuel of indirect demand, where the dominant contributions are the mining of the rare earth oxide ceria, the manufacturing of the solar concentration infrastructure, and the cleaning of the mirrors. The area-specific productivity is found to be 33 362 liters per hectare per year of jet fuel equivalents, where the land coverage is mainly due to the concentration of solar energy for heat and electricity. The water footprint and the land requirement of the solar thermochemical fuel pathway are larger than the best power-to-liquid pathways but an order of magnitude lower than the best biomass-to-liquid pathways. For the production of solar thermochemical fuels arid regions are best-suited, and for biofuels regions of a moderate and humid climate.

Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

PubMed

Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

2016-03-21

The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simunovic, Srdjan; Piro, Markus H.A.

Thermochimica is a software library that determines a unique combination of phases and their compositions at thermochemical equilibrium. Thermochimica can be used for stand-alone calculations or it can be directly coupled to other codes. This release of the software does not have a graphical user interface (GUI) and it can be executed from the command line or from an Application Programming Interface (API). Also, it is not intended for thermodynamic model development or for constructing phase diagrams. The main purpose of the software is to be directly coupled with a multi-physics code to provide material properties and boundary conditions formore » various physical phenomena. Significant research efforts have been dedicated to enhance computational performance through advanced algorithm development, such as improved estimation techniques and non-linear solvers. Various useful parameters can be provided as output from Thermochimica, such as: determination of which phases are stable at equilibrium, the mass of solution species and phases at equilibrium, mole fractions of solution phase constituents, thermochemical activities (which are related to partial pressures for gaseous species), chemical potentials of solution species and phases, and integral Gibbs energy (referenced relative to standard state). The overall goal is to provide an open source computational tool to enhance the predictive capability of multi-physics codes without significantly impeding computational performance.« less

User's Manual for the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA)

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Cheatwood, F. McNeil

1996-01-01

This user's manual provides detailed instructions for the installation and the application of version 4.1 of the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA). Also provides simulation of flow field in thermochemical nonequilibrium around vehicles traveling at hypersonic velocities through the atmosphere. Earlier versions of LAURA were predominantly research codes, and they had minimal (or no) documentation. This manual describes UNIX-based utilities for customizing the code for special applications that also minimize system resource requirements. The algorithm is reviewed, and the various program options are related to specific equations and variables in the theoretical development.

Experimental aspects of the thermochemical conversion of solar energy - Decarbonation of CaCO3

NASA Astrophysics Data System (ADS)

Flamant, G.; Hernandez, D.; Bonet, C.; Traverse, J.-P.

1980-01-01

The feasibility of thermochemical conversion of concentrated solar energy is investigated. Consideration is given to heterogeneous systems in the range 500-1500 C. A reaction volume is on a laboratory scale about 30 cu cm. An experimental set-up selected is a fluid bed and a rotary kiln. An endothermal reaction, namely, decarbonation of CaCO3, is selected as a possible application for solar power plants.

Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review

PubMed Central

Roeb, Martin; Neises, Martina; Monnerie, Nathalie; Call, Friedemann; Simon, Heike; Sattler, Christian; Schmücker, Martin; Pitz-Paal, Robert

2012-01-01

Thermochemical multistep water- and CO2-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO2 and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO2-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

Surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow

NASA Astrophysics Data System (ADS)

Yang, Xiaofeng; Gui, Yewei; Tang, Wei; Du, Yanxia; Liu, Lei; Xiao, Guangming; Wei, Dong

2018-06-01

This paper deals with the surface thermochemical effects on TPS-coupled aerothermodynamics in hypersonic Martian gas flow. An interface condition with finite-rate thermochemistry was established to balance the three-dimensional Navier-Stokes solver and TPS thermal response solver, and a series of coupled simulations of chemical non-equilibrium aerothermodynamics and structure heat transfer with various surface catalycities were performed for hypersonic Mars entries. The analysis of surface thermochemistry reveals that the surface chemical reactions have great contribution to aerodynamic heating, and the temperature-dependence of finite-rate catalysis highly influences the evolution of the coupling aerodynamic heating in the coupling process. For fixed free stream parameters with proper catalytic excitation energy, a "leap" phenomenon of the TPS-coupled heat flux with the coupling time appears in the initial stage of the coupling process, due to the strong thermochemical effects on the TPS surface.

Thermochemical pretreatments for enhancing succinic acid production from industrial hemp (Cannabis sativa L.).

PubMed

Gunnarsson, Ingólfur B; Kuglarz, Mariusz; Karakashev, Dimitar; Angelidaki, Irini

2015-04-01

The aim of this study was to develop an efficient thermochemical method for treatment of industrial hemp biomass, in order to increase its bioconversion to succinic acid. Industrial hemp was subjected to various thermochemical pretreatments using 0-3% H2SO4, NaOH or H2O2 at 121-180°C prior to enzymatic hydrolysis. The influence of the different pretreatments on hydrolysis and succinic acid production by Actinobacillus succinogenes 130Z was investigated in batch mode, using anaerobic bottles and bioreactors. Enzymatic hydrolysis and fermentation of hemp material pretreated with 3% H2O2 resulted in the highest overall sugar yield (73.5%), maximum succinic acid titer (21.9 g L(-1)), as well as the highest succinic acid yield (83%). Results obtained clearly demonstrated the impact of different pretreatments on the bioconversion efficiency of industrial hemp into succinic acid. Copyright © 2015. Published by Elsevier Ltd.

Thermochemical conversion of microalgal biomass into biofuels: a review.

PubMed

Chen, Wei-Hsin; Lin, Bo-Jhih; Huang, Ming-Yueh; Chang, Jo-Shu

2015-05-01

Following first-generation and second-generation biofuels produced from food and non-food crops, respectively, algal biomass has become an important feedstock for the production of third-generation biofuels. Microalgal biomass is characterized by rapid growth and high carbon fixing efficiency when they grow. On account of potential of mass production and greenhouse gas uptake, microalgae are promising feedstocks for biofuels development. Thermochemical conversion is an effective process for biofuel production from biomass. The technology mainly includes torrefaction, liquefaction, pyrolysis, and gasification. Through these conversion technologies, solid, liquid, and gaseous biofuels are produced from microalgae for heat and power generation. The liquid bio-oils can further be upgraded for chemicals, while the synthesis gas can be synthesized into liquid fuels. This paper aims to provide a state-of-the-art review of the thermochemical conversion technologies of microalgal biomass into fuels. Detailed conversion processes and their outcome are also addressed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1993-01-01

Computations are presented for one-dimensional, strong shock waves that are typical of those that form in front of a reentering spacecraft. The fluid mechanics and thermochemistry are modeled using two different approaches. The first employs traditional continuum techniques in solving the Navier-Stokes equations. The second-approach employs a particle simulation technique (the direct simulation Monte Carlo method, DSMC). The thermochemical models employed in these two techniques are quite different. The present investigation presents an evaluation of thermochemical models for nitrogen under hypersonic flow conditions. Four separate cases are considered. The cases are governed, respectively, by the following: vibrational relaxation; weak dissociation; strong dissociation; and weak ionization. In near-continuum, hypersonic flow, the nonequilibrium thermochemical models employed in continuum and particle simulations produce nearly identical solutions. Further, the two approaches are evaluated successfully against available experimental data for weakly and strongly dissociating flows.

Comparative studies on thermochemical characterization of corn stover pretreated by white-rot and brown-rot fungi.

PubMed

Zeng, Yelin; Yang, Xuewei; Yu, Hongbo; Zhang, Xiaoyu; Ma, Fuying

2011-09-28

The effects of white-rot and brown-rot fungal pretreatment on the chemical composition and thermochemical conversion of corn stover were investigated. Fungus-pretreated corn stover was analyzed by Fourier transform infrared spectroscopy and X-ray diffraction analysis to characterize the changes in chemical composition. Differences in thermochemical conversion of corn stover after fungal pretreatment were investigated using thermogravimetric and pyrolysis analysis. The results indicated that the white-rot fungus Irpex lacteus CD2 has great lignin-degrading ability, whereas the brown-rot fungus Fomitopsis sp. IMER2 preferentially degrades the amorphous regions of the cellulose. The biopretreatment favors thermal decomposition of corn stover. The weight loss of IMER2-treated acid detergent fiber became greater, and the oil yield increased from 32.7 to 50.8%. After CD2 biopretreatment, 58% weight loss of acid detergent lignin was achieved and the oil yield increased from 16.8 to 26.8%.

Thermochemical water decomposition. [hydrogen separation for energy applications

NASA Technical Reports Server (NTRS)

Funk, J. E.

1977-01-01

At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

The NATA code; theory and analysis. Volume 2: User's manual

NASA Technical Reports Server (NTRS)

Bade, W. L.; Yos, J. M.

1975-01-01

The NATA code is a computer program for calculating quasi-one-dimensional gas flow in axisymmetric nozzles and rectangular channels, primarily to describe conditions in electric archeated wind tunnels. The program provides solutions based on frozen chemistry, chemical equilibrium, and nonequilibrium flow with finite reaction rates. The shear and heat flux on the nozzle wall are calculated and boundary layer displacement effects on the inviscid flow are taken into account. The program contains compiled-in thermochemical, chemical kinetic and transport cross section data for high-temperature air, CO2-N2-Ar mixtures, helium, and argon. It calculates stagnation conditions on axisymmetric or two-dimensional models and conditions on the flat surface of a blunt wedge. Included in the report are: definitions of the inputs and outputs; precoded data on gas models, reactions, thermodynamic and transport properties of species, and nozzle geometries; explanations of diagnostic outputs and code abort conditions; test problems; and a user's manual for an auxiliary program (NOZFIT) used to set up analytical curvefits to nozzle profiles.

Development of efficient, integrated cellulosic biorefineries : LDRD final report.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Teh, Kwee-Yan; Hecht, Ethan S.; Shaddix, Christopher R.

2010-09-01

Cellulosic ethanol, generated from lignocellulosic biomass sources such as grasses and trees, is a promising alternative to conventional starch- and sugar-based ethanol production in terms of potential production quantities, CO{sub 2} impact, and economic competitiveness. In addition, cellulosic ethanol can be generated (at least in principle) without competing with food production. However, approximately 1/3 of the lignocellulosic biomass material (including all of the lignin) cannot be converted to ethanol through biochemical means and must be extracted at some point in the biochemical process. In this project we gathered basic information on the prospects for utilizing this lignin residue material inmore » thermochemical conversion processes to improve the overall energy efficiency or liquid fuel production capacity of cellulosic biorefineries. Two existing pretreatment approaches, soaking in aqueous ammonia (SAA) and the Arkenol (strong sulfuric acid) process, were implemented at Sandia and used to generated suitable quantities of residue material from corn stover and eucalyptus feedstocks for subsequent thermochemical research. A third, novel technique, using ionic liquids (IL) was investigated by Sandia researchers at the Joint Bioenergy Institute (JBEI), but was not successful in isolating sufficient lignin residue. Additional residue material for thermochemical research was supplied from the dilute-acid simultaneous saccharification/fermentation (SSF) pilot-scale process at the National Renewable Energy Laboratory (NREL). The high-temperature volatiles yields of the different residues were measured, as were the char combustion reactivities. The residue chars showed slightly lower reactivity than raw biomass char, except for the SSF residue, which had substantially lower reactivity. Exergy analysis was applied to the NREL standard process design model for thermochemical ethanol production and from a prototypical dedicated biochemical process, with process data supplied by a recent report from the National Research Council (NRC). The thermochemical system analysis revealed that most of the system inefficiency is associated with the gasification process and subsequent tar reforming step. For the biochemical process, the steam generation from residue combustion, providing the requisite heating for the conventional pretreatment and alcohol distillation processes, was shown to dominate the exergy loss. An overall energy balance with different potential distillation energy requirements shows that as much as 30% of the biomass energy content may be available in the future as a feedstock for thermochemical production of liquid fuels.« less

Dynamics of Compressible Convection and Thermochemical Mantle Convection

NASA Astrophysics Data System (ADS)

Liu, Xi

The Earth's long-wavelength geoid anomalies have long been used to constrain the dynamics and viscosity structure of the mantle in an isochemical, whole-mantle convection model. However, there is strong evidence that the seismically observed large low shear velocity provinces (LLSVPs) in the lowermost mantle are chemically distinct and denser than the ambient mantle. In this thesis, I investigated how chemically distinct and dense piles influence the geoid. I formulated dynamically self-consistent 3D spherical convection models with realistic mantle viscosity structure which reproduce Earth's dominantly spherical harmonic degree-2 convection. The models revealed a compensation effect of the chemically dense LLSVPs. Next, I formulated instantaneous flow models based on seismic tomography to compute the geoid and constrain mantle viscosity assuming thermochemical convection with the compensation effect. Thermochemical models reconcile the geoid observations. The viscosity structure inverted for thermochemical models is nearly identical to that of whole-mantle models, and both prefer weak transition zone. Our results have implications for mineral physics, seismic tomographic studies, and mantle convection modelling. Another part of this thesis describes analyses of the influence of mantle compressibility on thermal convection in an isoviscous and compressible fluid with infinite Prandtl number. A new formulation of the propagator matrix method is implemented to compute the critical Rayleigh number and the corresponding eigenfunctions for compressible convection. Heat flux and thermal boundary layer properties are quantified in numerical models and scaling laws are developed.

Solar thermochemical splitting of water to generate hydrogen

PubMed Central

Rao, C. N. R.; Dey, Sunita

2017-01-01

Solar photochemical means of splitting water (artificial photosynthesis) to generate hydrogen is emerging as a viable process. The solar thermochemical route also promises to be an attractive means of achieving this objective. In this paper we present different types of thermochemical cycles that one can use for the purpose. These include the low-temperature multistep process as well as the high-temperature two-step process. It is noteworthy that the multistep process based on the Mn(II)/Mn(III) oxide system can be carried out at 700 °C or 750 °C. The two-step process has been achieved at 1,300 °C/900 °C by using yttrium-based rare earth manganites. It seems possible to render this high-temperature process as an isothermal process. Thermodynamics and kinetics of H2O splitting are largely controlled by the inherent redox properties of the materials. Interestingly, under the conditions of H2O splitting in the high-temperature process CO2 can also be decomposed to CO, providing a feasible method for generating the industrially important syngas (CO+H2). Although carbonate formation can be addressed as a hurdle during CO2 splitting, the problem can be avoided by a suitable choice of experimental conditions. The choice of the solar reactor holds the key for the commercialization of thermochemical fuel production. PMID:28522461

Effects of combining ozone and hydrogren peroxide on tooth bleaching: A clinical study.

PubMed

Al-Omiri, Mahmoud K; Hassan, Ra'ed S Abul; AlZarea, Bader K; Lynch, Edward

2016-10-01

The purpose of this study was to evaluate the efficiency of bleaching after combining ozone and 38% H2O2 in comparison to the sole use of 38% H2O2. Consecutive 26 participants (13 males and 13 females) were recruited into this study. They were randomly allocated into 2 groups (n=13 for each group). In group 1 (test group); the participants' upper anterior teeth were treated with 38% H2O2 for 20min then the teeth were exposed to ozone for 60s (healOzone(®) X4, KaVo Dental, Biberach, Germany). In group 2 (controls); the upper anterior teeth were treated with 20min of 38% H2O2 only. The shade of teeth was evaluated by recording the L* a* b* values and Vita Classic shades at study baseline and after bleaching in both groups. The statistically significant changes were set at P≤0.05. Tooth sensitivity and teeth shades were comparable between groups at study baseline (p>0.05). Controls reported more tooth sensitivity following bleaching (p<0.001). Teeth achieved better Vita shades, higher L* values (lighter shades), and lower a* and b* values (lighter shades) after bleaching in both groups (P≤0.05). However, teeth bleached with H2O2 and ozone achieved better Vita shades, higher L* values and lower a* values (lighter shades) than those bleached with H2O2 alone (p<0.001). Changes in b* values were not significantly different between groups. Bleaching with 38% H2O2 for 20min followed by 60s of ozone application would result in teeth with lighter shades than bleaching with 38% H2O2 alone. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species.

PubMed

Klippenstein, Stephen J; Harding, Lawrence B; Ruscic, Branko

2017-09-07

The fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds to essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2 , CH 4 , H 2 O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zero-point energy, core-valence, relativistic, and diagonal Born-Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0-1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species

DOE PAGES

Klippenstein, Stephen J.; Harding, Lawrence B.; Ruscic, Branko

2017-07-31

Here, the fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds tomore » essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H 2, CH 4, H 2O, and NH 3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zeropoint energy, core–valence, relativistic, and diagonal Born–Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0–1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.« less

Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter

DOEpatents

Klausner, James F.; Petrasch, Joerg

2017-06-06

A solar thermochemical reactor contains an outer member, an inner member disposed within an outer member, wherein the outer member surrounds the inner member and wherein the outer member has an aperture for receiving solar radiation. An inner cavity and an outer cavity are formed by the inner member and outer member and a reactive material that is capable of being magnetically stabilized is disposed in the outer cavity between the inner member and the outer member.

Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werner, R.W.

1982-11-01

This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

New developments of the CARTE thermochemical code: A two-phase equation of state for nanocarbons

NASA Astrophysics Data System (ADS)

Dubois, Vincent; Pineau, Nicolas

2016-01-01

We developed a new equation of state (EOS) for nanocarbons in the thermodynamic range of high explosives detonation products (up to 50 GPa and 4000 K). This EOS was fitted to an extensive database of thermodynamic properties computed by molecular dynamics simulations of nanodiamonds and nano-onions with the LCBOPII potential. We reproduced the detonation properties of a variety of high explosives with the CARTE thermochemical code, including carbon-poor and carbon-rich explosives, with excellent accuracy.

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

DOE PAGES

Paye, Julie M. D.; Guseva, Anna; Hammer, Sarah K.; ...

2016-01-12

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.

High Efficiency Solar Thermochemical Reactor for Hydrogen Production.

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDaniel, Anthony H.

2017-09-30

This research and development project is focused on the advancement of a technology that produces hydrogen at a cost that is competitive with fossil-based fuels for transportation. A twostep, solar-driven WS thermochemical cycle is theoretically capable of achieving an STH conversion ratio that exceeds the DOE target of 26% at a scale large enough to support an industrialized economy [1]. The challenge is to transition this technology from the laboratory to the marketplace and produce hydrogen at a cost that meets or exceeds DOE targets.

Silicon materials task of the low cost solar array project. Phase 3: Effect of impurities and processing on silicon solar cells

NASA Technical Reports Server (NTRS)

Hopkins, R. H.; Davis, J. R.; Blais, P. D.; Rohatgi, A.; Campbell, R. B.; Rai-Choudhury, P.; Mollenkopf, H. C.; Mccormick, J. R.

1979-01-01

The 13th quarterly report of a study entitled an Investigation of the Effects of Impurities and Processing on Silicon Solar Cells is given. The objective of the program is to define the effects of impurities, various thermochemical processes and any impurity-process interactions on the performance of terrestrial silicon solar cells. The Phase 3 program effort falls in five areas: (1) cell processing studies; (2) completion of the data base and impurity-performance modeling for n-base cells; (3) extension of p-base studies to include contaminants likely to be introduced during silicon production, refining or crystal growth; (4) anisotropy effects; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells. The quarterly activities for this report focus on tasks (1), (3) and (4).

A kinetic and thermochemical database for organic sulfur and oxygen compounds.

PubMed

Class, Caleb A; Aguilera-Iparraguirre, Jorge; Green, William H

2015-05-28

Potential energy surfaces and reaction kinetics were calculated for 40 reactions involving sulfur and oxygen. This includes 11 H2O addition, 8 H2S addition, 11 hydrogen abstraction, 7 beta scission, and 3 elementary tautomerization reactions, which are potentially relevant in the combustion and desulfurization of sulfur compounds found in various fuel sources. Geometry optimizations and frequencies were calculated for reactants and transition states using B3LYP/CBSB7, and potential energies were calculated using CBS-QB3 and CCSD(T)-F12a/VTZ-F12. Rate coefficients were calculated using conventional transition state theory, with corrections for internal rotations and tunneling. Additionally, thermochemical parameters were calculated for each of the compounds involved in these reactions. With few exceptions, rate parameters calculated using the two potential energy methods agreed reasonably, with calculated activation energies differing by less than 5 kJ mol(-1). The computed rate coefficients and thermochemical parameters are expected to be useful for kinetic modeling.

TEA: A Code Calculating Thermochemical Equilibrium Abundances

NASA Astrophysics Data System (ADS)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass.

PubMed

Wang, Zhaojiang; Qin, Menghua; Zhu, J Y; Tian, Guoyu; Li, Zongquan

2013-02-01

Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical-biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by dilute acid (DA) and sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL). It was observed that the structure deconstruction of rejects by physical refining was indispensable to effective bioconversion but more energy intensive than that of thermochemically pretreated biomass. Fortunately, the energy consumption was compensated by the reduced enzyme dosage and the elevated ethanol yield. Furthermore, adjustment of disk-plates gap led to reduction in energy consumption with negligible influence on ethanol yield. In this context, energy efficiency up to 717.7% was achieved for rejects, much higher than that of SPORL sample (283.7%) and DA sample (152.8%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Solar hydrogen production with cerium oxides thermochemical cycle

NASA Astrophysics Data System (ADS)

Binotti, Marco; Di Marcoberardino, Gioele; Biassoni, Mauro; Manzolini, Giampaolo

2017-06-01

This paper discusses the hydrogen production using a solar driven thermochemical cycle. The thermochemical cycle is based on nonstoichiometric cerium oxides redox and the solar concentration system is a solar dish. Detailed optical and redox models were developed to optimize the hydrogen production performance as function of several design parameters (i.e. concentration ratio, reactor pressures and temperatures) The efficiency of the considered technology is compared against two commercially available technologies namely PV + electrolyzer and Dish Stirling + electrolyzer. Results show that solar-to-fuel efficiency of 21.2% can be achieved at design condition assuming a concentration ratio around 5000, reduction and oxidation temperatures of 1500°C and 1275 °C. When moving to annual performance, the annual yield of the considered approach can be as high as 16.7% which is about 43% higher than the best competitive technology. The higher performance implies that higher installation costs around 40% can be accepted for the innovative concept to achieve the same cost of hydrogen.

Thermochemical hydrogen production based on magnetic fusion

NASA Astrophysics Data System (ADS)

Krikorian, O. H.; Brown, L. C.

Preliminary results of a DoE study to define the configuration and production costs for a Tandem Mirror Reactor (TMR) heat source H2 fuel production plant are presented. The TMR uses the D-T reaction to produce thermal energy and dc electrical current, with an Li blanket employed to breed more H-3 for fuel. Various blanket designs are being considered, and the coupling of two of them, a heat pipe blanket to a Joule-boosted decomposer, and a two-temperature zone blanket to a fluidized bed decomposer, are discussed. The thermal energy would be used in an H2SO4 thermochemical cycler to produce the H2. The Joule-boosted decomposer, involving the use of electrically heated commercial SiC furnace elements to transfer process heat to the thermochemical H2 cycle, is found to yield H2 fuel at a cost of $12-14/GJ, which is the projected cost of fossil fuels in 30-40 yr, when the TMR H2 production facility would be operable.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver, E-mail: jasmina@physics.ucf.edu

2016-07-01

We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature–pressure pairs. We tested the code against the method of Burrows and Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows and Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but withmore » higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.« less

Potential for thermochemical conversion of biomass residues from the integrated sugar-ethanol process - Fate of ash and ash-forming elements.

PubMed

Dirbeba, Meheretu Jaleta; Brink, Anders; DeMartini, Nikolai; Zevenhoven, Maria; Hupa, Mikko

2017-06-01

In this work, potential for thermochemical conversion of biomass residues from an integrated sugar-ethanol process and the fate of ash and ash-forming elements in the process are presented. Ash, ash-forming elements, and energy flows in the process were determined using mass balances and analyses of eight different biomass samples for ash contents, elemental compositions, and heating values. The results show that the ash content increases from the sugarcane to the final residue, vinasse. The cane straw, which is left in the field, contains one-third of the energy and 25% of the K and Cl while the vinasse contains 2% of the energy and 40% of the K and Cl in the cane. K and Cl in biomass fuels cause corrosion and fouling problems in boilers and gasifiers. Over 85% of these elements in the straw are water soluble indicating that water leaching would improve it for utilization in thermochemical conversion. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modeling Hemispheric Detonation Experiments in 2-Dimensions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Howard, W M; Fried, L E; Vitello, P A

2006-06-22

Experiments have been performed with LX-17 (92.5% TATB and 7.5% Kel-F 800 binder) to study scaling of detonation waves using a dimensional scaling in a hemispherical divergent geometry. We model these experiments using an arbitrary Lagrange-Eulerian (ALE3D) hydrodynamics code, with reactive flow models based on the thermo-chemical code, Cheetah. The thermo-chemical code Cheetah provides a pressure-dependent kinetic rate law, along with an equation of state based on exponential-6 fluid potentials for individual detonation product species, calibrated to high pressures ({approx} few Mbars) and high temperatures (20000K). The parameters for these potentials are fit to a wide variety of experimental data,more » including shock, compression and sound speed data. For the un-reacted high explosive equation of state we use a modified Murnaghan form. We model the detonator (including the flyer plate) and initiation system in detail. The detonator is composed of LX-16, for which we use a program burn model. Steinberg-Guinan models5 are used for the metal components of the detonator. The booster and high explosive are LX-10 and LX-17, respectively. For both the LX-10 and LX-17, we use a pressure dependent rate law, coupled with a chemical equilibrium equation of state based on Cheetah. For LX-17, the kinetic model includes carbon clustering on the nanometer size scale.« less

High-temperature thermochemical energy storage based on redox reactions using Co-Fe and Mn-Fe mixed metal oxides

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-09-01

Metal oxides are potential materials for thermochemical heat storage via reversible endothermal/exothermal redox reactions, and among them, cobalt oxide and manganese oxide are attracting attention. The synthesis of mixed oxides is considered as a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering issues, and the materials potential for thermochemical heat storage application needs to be assessed. This work proposes a study combining thermodynamic calculations and experimental measurements by simultaneous thermogravimetric analysis and calorimetry, in order to identify the impact of iron oxide addition to Co and Mn-based oxides. Fe addition decreased the redox activity and energy storage capacity of Co3O4/CoO, whereas the reaction rate, reversibility and cycling stability of Mn2O3/Mn3O4 was significantly enhanced with added Fe amounts above 15 mol%, and the energy storage capacity was slightly improved. The formation of a reactive cubic spinel explained the improved re-oxidation yield of Mn-based oxides that could be cycled between bixbyite and cubic spinel phases, whereas a low reactive tetragonal spinel phase showing poor re-oxidation was formed below 15 mol% Fe. Thermodynamic equilibrium calculations predict accurately the behavior of both systems. The possibility to identify other suitable mixed oxides becomes conceivable, by enabling the selection of transition metal additives for tuning the redox properties of mixed metal oxides destined for thermochemical energy storage applications.

Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry

DOE PAGES

Ruscic, Branko

2015-03-31

Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE 298) and bond dissociation energies at 0 K (D 0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CH n, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C 2H n, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHmore » n, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO 2 and H 2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.« less

FY06 L2C2 HE program report Zaug et al.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zaug, J M; Crowhurst, J C; Howard, W M

2008-08-01

The purpose of this project is to advance the improvement of LLNL thermochemical computational models that form the underlying basis or input for laboratory hydrodynamic simulations. Our general work approach utilizes, by design, tight experimental-theoretical research interactions that allow us to not empirically, but rather more scientifically improve LLNL computational results. The ultimate goal here is to confidently predict through computer models, the performance and safety parameters of currently maintained, modified, and newly designed stockpile systems. To attain our goal we make relevant experimental measurements on candidate detonation products constrained under static high-pressure and temperature conditions. The reduced information frommore » these measurements is then used to construct analytical forms that describe the potential surface (repulsive energy as a function of interatomic separation distance) of single and mixed fluid or detonation product species. These potential surface shapes are also constructed using input from well-trusted shock wave physics and assorted thermodynamic data available in the open literature. Our potential surfaces permit one to determine the equations of state (P,V,T), the equilibrium chemistry, phase, and chemical interactions of detonation products under a very wide range of extreme pressure temperature conditions. Using our foundation of experimentally refined potential surfaces we are in a position to calculate, with confidence, the energetic output and chemical speciation occurring from a specific combustion and/or detonation reaction. The thermochemical model we developed and use for calculating the equilibrium chemistry, kinetics, and energy from ultrafast processes is named 'Cheetah'. Computational results from our Cheetah code are coupled to laboratory ALE3D hydrodynamic simulation codes where the complete response behavior of an existing or proposed system is ultimately predicted. The Cheetah thermochemical code is also used by well over 500 U.S. government DoD and DOE community users who calculate the chemical properties of detonated high explosives, propellants, and pyrotechnics. To satisfy the growing needs of LLNL and the general user community we continue to improve the robustness of our Cheetah code. The P-T range of current speed of sound experiments will soon be extended by a factor of four and our recently developed technological advancements permit us to, for the first time, study any chemical specie or fluid mixture. New experiments will focus on determining the miscibility or coexistence curves of detonation product mixtures. Our newly constructed ultrafast laser diagnostics will permit us to determine what chemical species exist under conditions approaching Chapman-Jouguet (CJ) detonation states. Furthermore we will measure the time evolution of candidate species and use our chemical kinetics data to develop new and validate existing rate laws employed in future versions of our Cheetah thermochemical code.« less

Mathematical Models of Human Hematopoiesis Following Acute Radiation Exposure

DTIC Science & Technology

2014-05-01

Agency 8725 John J . Kingman Road, MS 6201 Fort Belvoir, VA 22060-6201 T E C H N IC A L R E P O R T DTRA...eV) 1.602 177 × 10–19 joule ( J ) erg 1 × 10–7 joule ( J ) kiloton (kT) (TNT equivalent) 4.184 × 1012 joule ( J ) British thermal unit (Btu...thermochemical) 1.054 350 × 103 joule ( J ) foot-pound-force (ft lbf) 1.355 818 joule ( J ) calorie (cal) (thermochemical) 4.184 joule ( J ) Pressure

Thermochemical energy storage for a lunar base

NASA Technical Reports Server (NTRS)

Perez-Davis, Marla E.; Mckissock, Barbara I.; Difilippo, Frank

1992-01-01

A thermochemical solar energy storage concept involving the reversible reaction CaO + H2O yields Ca(OH)2 is proposed as a power system element for a lunar base. The operation and components of such a system are described. The CaO/H2O system is capable of generating electric power during both the day and night. Mass of the required amount of CaO is neglected since it is obtained from lunar soil. Potential technical problems, such as reactor design and lunar soil processing, are reviewed.

The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.

1990-01-01

A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

Thermochemical water decomposition processes

NASA Technical Reports Server (NTRS)

Chao, R. E.

1974-01-01

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Methane-methanol cycle for the thermochemical production of hydrogen

DOEpatents

Dreyfuss, Robert M.; Hickman, Robert G.

1976-01-01

A thermochemical reaction cycle for the generation of hydrogen from water comprising the following sequence of reactions wherein M represents a metal: CH.sub.4 + H.sub.2 O .fwdarw. CO + 3H.sub.2 (1) co + 2h.sub.2 .fwdarw. ch.sub.3 oh (2) ch.sub.3 oh + so.sub.2 + mo .fwdarw. mso.sub.4 + ch.sub.4 (3) mso.sub.4 .fwdarw. mo + so.sub.2 + 1/2o.sub.2 (4) the net reaction is the decomposition of water into hydrogen and oxygen.

Solar thermochemical processing system and method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wegeng, Robert S.; Humble, Paul H.; Krishnan, Shankar

A solar thermochemical processing system is disclosed. The system includes a first unit operation for receiving concentrated solar energy. Heat from the solar energy is used to drive the first unit operation. The first unit operation also receives a first set of reactants and produces a first set of products. A second unit operation receives the first set of products from the first unit operation and produces a second set of products. A third unit operation receives heat from the second unit operation to produce a portion of the first set of reactants.

Development and testing of a numerical simulation method for thermally nonequilibrium dissociating flows in ANSYS Fluent

NASA Astrophysics Data System (ADS)

Shoev, G. V.; Bondar, Ye. A.; Oblapenko, G. P.; Kustova, E. V.

2016-03-01

Various issues of numerical simulation of supersonic gas flows with allowance for thermochemical nonequilibrium on the basis of fluid dynamic equations in the two-temperature approximation are discussed. The computational tool for modeling flows with thermochemical nonequilibrium is the commercial software package ANSYS Fluent with an additional userdefined open-code module. A comparative analysis of results obtained by various models of vibration-dissociation coupling in binary gas mixtures of nitrogen and oxygen is performed. Results of numerical simulations are compared with available experimental data.

Tuning the Thermochemical Properties of Oxonol Dyes for Digital Versatile Disc Recordable: Reduction of Thermal Interference in High-Speed Recording

NASA Astrophysics Data System (ADS)

Morishima, Shin-Ichi; Wariishi, Koji; Mikoshiba, Hisashi; Inagaki, Yoshio; Shibata, Michihiro; Hashimoto, Hirokazu; Kubo, Hiroshi

To reduce thermal interference between adjacent recording marks on a recordable digital versatile disc, we examined the thermochemical behavior of oxonol dyes for digital versatile disc recordable (DVD-R). We found that oxonol dyes with Meldrum's acid skeleton exhibited an abrupt reduction in weight with increasing temperature without generating excessive heat that is the fundamental cause of thermal interference. DVD-R with the oxonol dyes suppressed fluctuation in the shapes of recorded marks, thereby attaining compatibility with high-speed recording.

Laser beam heat method reported

NASA Astrophysics Data System (ADS)

Tsuchiya, Hachiro; Goto, Hidekazu

1988-07-01

An outline of research involving the processing method utilizing laser-induced thermochemistry was presented, with the CO2 laser processing of ceramics in CF4 gas used as a practical processing example. It has become clear that it will be possible to conduct laser proccessing of ceramics with high efficiency and high precision by utilizing the thermochemical processes, but it is not believed that the present method is the best one and it is not clear that it can be applied to commercial processing. It is thought that the processing characteristics of this method will be greatly changed by the combination of the atmospheric gas and the material, and it is important to conduct tests on various combinations. However, it is believed that the improvement and development will become possible by theoretically confirming the basic process of the processing, especially of the the thermochemical process between the solid surface and the atmospheric gas molecule. Actually, it is believed that the thermochemical process on the solid surface is quite complicated. For example, it was confirmed that when thermochemical processing the Si monocrystal in the CF4 gas, the processing speed would change by at least 10 times through changing the gas pressure and the mixing O2 gas density. However, conversely speaking, it is believed that the fact that this method is complicated, with many unexplained points and room for research, conceals the possibility of its being applied to various fields, and also, in this sense, the quantitative confirmation of its basic process in an important problem to be solved in the future.

Copper(II)-mediated thermolysis of alginates: a model kinetic study on the influence of metal ions in the thermochemical processing of macroalgae

PubMed Central

Rowbotham, J. S.; Dyer, P. W.; Greenwell, H. C.; Selby, D.; Theodorou, M. K.

2013-01-01

Thermochemical processing methods such as pyrolysis are of growing interest as a means of converting biomass into fuels and commodity chemicals in a sustainable manner. Macroalgae, or seaweed, represent a novel class of feedstock for pyrolysis that, owing to the nature of the environments in which they grow coupled with their biochemistry, naturally possess high metal contents. Although the impact of metals upon the pyrolysis of terrestrial biomass is well documented, their influence on the thermochemical conversion of marine-derived feeds is largely unknown. Furthermore, these effects are inherently difficult to study, owing to the heterogeneous character of natural seaweed samples. The work described in this paper uses copper(II) alginate, together with alginic acid and sodium alginate as model compounds for exploring the effects of metals upon macroalgae thermolysis. A thermogravimetric analysis–Fourier transform infrared spectroscopic study revealed that, unusually, Cu2+ ions promote the onset of pyrolysis in the alginate polymer, with copper(II) alginate initiating rapid devolatilization at 143°C, 14°C lower than alginic acid and 61°C below the equivalent point for sodium alginate. Moreover, this effect was mirrored in a sample of wild Laminaria digitata that had been doped with Cu2+ ions prior to pyrolysis, thus validating the use of alginates as model compounds with which to study the thermolysis of macroalgae. These observations indicate the varying impact of different metal species on thermochemical behaviour of seaweeds and offer an insight into the pyrolysis of brown macroalgae used in phytoremediation of metal-containing waste streams. PMID:24427515

The thermochemical structure and evolution of Earth's mantle: constraints and numerical models.

PubMed

Tackley, Paul J; Xie, Shunxing

2002-11-15

Geochemical observations place several constraints on geophysical processes in the mantle, including a requirement to maintain several distinct reservoirs. Geophysical constraints limit plausible physical locations of these reservoirs to a thin basal layer, isolated deep 'piles' of material under large-scale mantle upwellings, high-viscosity blobs/plums or thin strips throughout the mantle, or some combination of these. A numerical model capable of simulating the thermochemical evolution of the mantle is introduced. Preliminary simulations are more differentiated than Earth but display some of the proposed thermochemical processes, including the generation of a high-mu mantle reservoir by recycling of crust, and the generation of a high-(3)He/(4)He reservoir by recycling of residuum, although the resulting high-(3)He/(4)He material tends to aggregate near the top, where mid-ocean-ridge melting should sample it. If primitive material exists as a dense basal layer, it must be much denser than subducted crust in order to retain its primitive (e.g. high-(3)He) signature. Much progress is expected in the near future.

Comparison of seven types of thermo-chemical pretreatments on the structural features and anaerobic digestion of sunflower stalks.

PubMed

Monlau, F; Barakat, A; Steyer, J P; Carrere, H

2012-09-01

Sunflower stalks can be used for the production of methane, but their recalcitrant structure requires the use of thermo-chemical pretreatments. Two thermal (55 and 170°C) and five thermo-chemical pretreatments (NaOH, H(2)O(2), Ca(OH)(2), HCl and FeCl(3)) were carried out, followed by anaerobic digestion. The highest methane production (259 ± 6 mL CH(4)g(-1) VS) was achieved after pretreatment at 55°C with 4% NaOH for 24h. Acidic pretreatments at 170°C removed more than 90% of hemicelluloses and uronic acids whereas alkaline and oxidative pretreatments were more effective in dissolving lignin. However, no pretreatment was effective in reducing the crystallinity of cellulose. Methane production rate was positively correlated with the amount of solubilized matter whereas methane potential was negatively correlated with the amount of lignin. Considering that the major challenge is obtaining increased methane potential, alkaline pretreatments can be recommended in order to optimize the anaerobic digestion of lignocellulosic substrates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermochemistry and vertical mixing in the tropospheres of Uranus and Neptune: How convection inhibition can affect the derivation of deep oxygen abundances

NASA Astrophysics Data System (ADS)

Cavalié, T.; Venot, O.; Selsis, F.; Hersant, F.; Hartogh, P.; Leconte, J.

2017-07-01

Thermochemical models have been used in the past to constrain the deep oxygen abundance in the gas and ice giant planets from tropospheric CO spectroscopic measurements. Knowing the oxygen abundance of these planets is a key to better understand their formation. These models have widely used dry and/or moist adiabats to extrapolate temperatures from the measured values in the upper troposphere down to the level where the thermochemical equilibrium between H2O and CO is established. The mean molecular mass gradient produced by the condensation of H2O stabilizes the atmosphere against convection and results in a vertical thermal profile and H2O distribution that departs significantly from previous estimates. We revisit O/H estimates using an atmospheric structure that accounts for the inhibition of the convection by condensation. We use a thermochemical network and the latest observations of CO in Uranus and Neptune to calculate the internal oxygen enrichment required to satisfy both these new estimates of the thermal profile and the observations. We also present the current limitations of such modeling.

Biochar potential evaluation of palm oil wastes through slow pyrolysis: Thermochemical characterization and pyrolytic kinetic studies.

PubMed

Lee, Xin Jiat; Lee, Lai Yee; Gan, Suyin; Thangalazhy-Gopakumar, Suchithra; Ng, Hoon Kiat

2017-07-01

This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin -1 N 2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg -1 ) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential. Copyright © 2017 Elsevier Ltd. All rights reserved.

Solar Thermochemical Energy Storage Through Carbonation Cycles of SrCO3/SrO Supported on SrZrO3.

PubMed

Rhodes, Nathan R; Barde, Amey; Randhir, Kelvin; Li, Like; Hahn, David W; Mei, Renwei; Klausner, James F; AuYeung, Nick

2015-11-01

Solar thermochemical energy storage has enormous potential for enabling cost-effective concentrated solar power (CSP). A thermochemical storage system based on a SrO/SrCO3 carbonation cycle offers the ability to store and release high temperature (≈1200 °C) heat. The energy density of SrCO3/SrO systems supported by zirconia-based sintering inhibitors was investigated for 15 cycles of exothermic carbonation at 1150 °C followed by decomposition at 1235 °C. A sample with 40 wt % of SrO supported by yttria-stabilized zirconia (YSZ) shows good energy storage stability at 1450 MJ m(-3) over fifteen cycles at the same cycling temperatures. After further testing over 45 cycles, a decrease in energy storage capacity to 1260 MJ m(-3) is observed during the final cycle. The decrease is due to slowing carbonation kinetics, and the original value of energy density may be obtained by lengthening the carbonation steps. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ability of thermochemical calculation to treat organic peroxides

NASA Astrophysics Data System (ADS)

Osmont, Antoine; Baudin, Gérard; Genetier, Marc

2017-06-01

Since 3 years, the CEA Gramat is developing a new thermochemical code, called SIAME, funded by DGA to help French defense industry at conceiving new explosives compositions. It enables the calculation of CJ detonation and deflagration points and combustion of explosives. The accuracy of the code has been checked on several compositions containing PETN, RDX, HMX, TNT, NTO. The error on the velocity of detonation is 3%. To enlarge the domain of validity of the code, organic peroxides have been considered. It is known that thermochemical simulation is in failure regarding compounds as simple as hydrogen peroxide. The computed velocity of detonation is 5720 m/s when shock planar impact gives 6150 m/s. The same discrepancy is found for TATP, with a calculated value at 5870 m/s when 5290 has been measured. Detonation velocity of TATP has been measured at two different densities. These velocities agree with other published values. A closer look at the enthalpy of formation of TATP has revealed that it comes from an article of 1932. Ab initio computations have given a totally different value, leading to better agreement with experiment.

Uncertainty quantification of crustal scale thermo-chemical properties in Southeast Australia

NASA Astrophysics Data System (ADS)

Mather, B.; Moresi, L. N.; Rayner, P. J.

2017-12-01

The thermo-chemical properties of the crust are essential to understanding the mechanical and thermal state of the lithosphere. The uncertainties associated with these parameters are connected to the available geophysical observations and a priori information to constrain the objective function. Often, it is computationally efficient to reduce the parameter space by mapping large portions of the crust into lithologies that have assumed homogeneity. However, the boundaries of these lithologies are, in themselves, uncertain and should also be included in the inverse problem. We assimilate geological uncertainties from an a priori geological model of Southeast Australia with geophysical uncertainties from S-wave tomography and 174 heat flow observations within an adjoint inversion framework. This reduces the computational cost of inverting high dimensional probability spaces, compared to probabilistic inversion techniques that operate in the `forward' mode, but at the sacrifice of uncertainty and covariance information. We overcome this restriction using a sensitivity analysis, that perturbs our observations and a priori information within their probability distributions, to estimate the posterior uncertainty of thermo-chemical parameters in the crust.

Nonmetallic materials handbook. Volume 2: Epoxy and silicone materials

NASA Technical Reports Server (NTRS)

Podlaseck, S. E.

1982-01-01

Chemical and physical property test data obtained during qualification and receiving inspection testing of nonmetallic materials for the Viking Mars Lander program is presented. Thermochemical data showing degradation as a function of temperature from room temperature through 773 K is included. These data include activation energies for thermal degradation, rate constants, and exo- and/or endotherms. Thermal degradations carried out under vacuum include mass spectral data taken simultaneously during the decomposition. Many materials have supporting data such as condensation rates of degassed products and isothermal weight loss. Changes in mechanical, electrical, and thermal properties after exposure to 408 K in nitrogen for times ranging from 380 to 570 hours are included for many materials.

Thermochemical and Physical Properties of Fluids, Lubricants and Related Materials. Delivery Order 0001 : Improved Methods Development for Determining Thermophysical and Thermochemical Properties of Fluids, Lubricants and Related Materials

DTIC Science & Technology

2008-07-01

PRF-5606H, ...................76 FTM 791C, method 36003) 168 hrs. @ 70ºC using NBR -L (AMS3217/2B Rubber specimens. 42. MLO-06...0275: Rubber Swell Test (MIL-PRF-5606H, .................77 FTM 791C, method 3603) 168 hrs. @ 70ºC using NBR -L...NUMBER MLO-05-421 Rubber Swell Test (MIL-PRF-5606H, FTM 791C, method 36003) 168 Hours @ 70°C (158°F) using NBR -L(AMS 3217/2B) rubber specimens

General Model for Multicomponent Ablation Thermochemistry

NASA Technical Reports Server (NTRS)

Milos, Frank S.; Marschall, Jochen; Rasky, Daniel J. (Technical Monitor)

1994-01-01

A previous paper (AIAA 94-2042) presented equations and numerical procedures for modeling the thermochemical ablation and pyrolysis of thermal protection materials which contain multiple surface species. This work describes modifications and enhancements to the Multicomponent Ablation Thermochemistry (MAT) theory and code for application to the general case which includes surface area constraints, rate limited surface reactions, and non-thermochemical mass loss (failure). Detailed results and comparisons with data are presented for the Shuttle Orbiter reinforced carbon-carbon oxidation protection system which contains a mixture of sodium silicate (Na2SiO3), silica (SiO2), silicon carbide (SiC), and carbon (C).

Corn fiber hulls as a food additive or animal feed

DOEpatents

Abbas, Charles; Beery, Kyle E.; Cecava, Michael J.; Doane, Perry H.

2010-12-21

The present invention provides a novel animal feed or food additive that may be made from thermochemically hydrolyzed, solvent-extracted corn fiber hulls. The animal feed or food additive may be made, for instance, by thermochemically treating corn fiber hulls to hydrolyze and solubilize the hemicellulose and starch present in the corn fiber hulls to oligosaccharides. The residue may be extracted with a solvent to separate the oil from the corn fiber, leaving a solid residue that may be prepared, for instance by aggolmerating, and sold as a food additive or an animal feed.

Predicting radiative heat transfer in thermochemical nonequilibrium flow fields. Theory and user's manual for the LORAN code

NASA Technical Reports Server (NTRS)

Chambers, Lin Hartung

1994-01-01

The theory for radiation emission, absorption, and transfer in a thermochemical nonequilibrium flow is presented. The expressions developed reduce correctly to the limit at equilibrium. To implement the theory in a practical computer code, some approximations are used, particularly the smearing of molecular radiation. Details of these approximations are presented and helpful information is included concerning the use of the computer code. This user's manual should benefit both occasional users of the Langley Optimized Radiative Nonequilibrium (LORAN) code and those who wish to use it to experiment with improved models or properties.

Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.

System for thermochemical hydrogen production

DOEpatents

Werner, R.W.; Galloway, T.R.; Krikorian, O.H.

1981-05-22

Method and apparatus are described for joule boosting a SO/sub 3/ decomposer using electrical instead of thermal energy to heat the reactants of the high temperature SO/sub 3/ decomposition step of a thermochemical hydrogen production process driven by a tandem mirror reactor. Joule boosting the decomposer to a sufficiently high temperature from a lower temperature heat source eliminates the need for expensive catalysts and reduces the temperature and consequent materials requirements for the reactor blanket. A particular decomposer design utilizes electrically heated silicon carbide rods, at a temperature of 1250/sup 0/K, to decompose a cross flow of SO/sub 3/ gas.

Generation of metallic plasmon nanostructures in a thin transparent photosensitive copper oxide film by femtosecond thermochemical decomposition

NASA Astrophysics Data System (ADS)

Danilov, P. A.; Zayarny, D. A.; Ionin, A. A.; Kudryashov, S. I.; Litovko, E. P.; Mel'nik, N. N.; Rudenko, A. A.; Saraeva, I. N.; Umanskaya, S. P.; Khmelnitskii, R. A.

2017-09-01

Irradiation of optically transparent copper (I) oxide film covering a glass substrate with a tightly focused femtosecond laser pulses in the pre-ablation regime leads to film reduction to a metallic colloidal state via a single-photon absorption and its subsequent thermochemical decomposition. This effect was demonstrated by the corresponding measurement of the extinction spectrum in visible spectral range. The laser-induced formation of metallic copper nanoparticles in the focal region inside the bulk oxide film allows direct recording of individual thin-film plasmon nanostructures and optical-range metasurfaces.

Study of TLIPSS formation on different metals and alloys and their selective etching

NASA Astrophysics Data System (ADS)

Dostovalov, Alexandr V.; Korolkov, Victor P.; Terentiev, Vadim S.; Okotrub, Konstantin A.; Dultsev, Fedor N.; Nemykin, Anton; Babin, Sergey A.

2017-02-01

Experimental investigation of thermochemical laser-induced periodic surface structures (TLIPSS) formation on metal films (Ti, Cr, Ni, NiCr) at different processing conditions is presented. The hypothesis that the TLIPSS formation depends significantly on parabolic rate constant for oxide thin film growth is discussed. Evidently, low value of this parameter for Ni is the reason of TLIPSS absence on Ni and NiCr film with low Cr content. The effect of simultaneous ablative (with period ≍λ) and thermochemical (with period ≍λ) LIPSS formation was observed. The formation of structures after TLIPSS selective etching was demonstrated.

Thermochemical generation of hydrogen

NASA Technical Reports Server (NTRS)

Lawson, D. D.; Petersen, G. R. (Inventor)

1982-01-01

The direct fluid contact heat exchange with H2SO4 at about 330 C prior to high temperature decomposition at about 830 C in the oxygen release step of several thermochemical cycles for splitting water into hydrogen and oxygen provides higher heat transfer rates, savings in energy and permits use of cast vessels rather than expensive forged alloy indirect heat exchangers. Among several candidate perfluorocarbon liquids tested, only perfluoropropylene oxide polymers having a degree of polymerization from about 10 to 60 were chemically stable, had low miscibility and vapor pressure when tested with sulfuric acid at temperatures from 300 C to 400 C.

Oxidative vaporization kinetics of Cr2O3 in oxygen from 1000 to 1300 C

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at a pressure of 0.115 Torr for temperatures from 1000 to 1300 C. Reaction controlled rates were obtained from experimental rates by a gold calibration technique, and these rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporization reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data using boundary-layer theory.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites ofmore » the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H{sub 2}O splitting is also achieved by the use of the Mn{sub 3}O{sub 4}-sodium carbonate system. • Thermochemical splitting of CO{sub 2} and H{sub 2}O using perovskite oxides is explained. • Mn based perovskites.« less

Interfacial Reaction Studies Using ONIOM

NASA Technical Reports Server (NTRS)

Cardelino, Beatriz H.

2003-01-01

In this report, we focus on the calculations of the energetics and chemical kinetics of heterogeneous reactions for Organometallic vapor phase epitaxy (OMVPE). The work described in this report builds upon our own previous thermochemical and chemical kinetics studies. The first of these articles refers to the prediction of thermochemical properties, and the latter one deals with the prediction of rate constants for gaseous homolytic dissociation reactions. The calculations of this investigation are at the microscopic level. The systems chosen consisted of a gallium nitride (GaN) substrate, and molecular nitrogen (N2) and ammonia (NH3) as adsorbants. The energetics for the adsorption and the adsorbant dissociation processes were estimated, and reaction rate constants for the dissociation reactions of free and adsorbed molecules were predicted. The energetics for substrate decomposition was also computed. The ONIOM method, implemented in the Gaussian98 program, was used to perform the calculations. This approach has been selected since it allows dividing the system into two layers that can be treated at different levels of accuracy. The atoms of the substrate were modeled using molecular mechanics6 with universal force fields, whereas the adsorbed molecules were approximated using quantum mechanics, based on density functional theory methods with B3LYP functionals and 6-311G(d,p) basis sets. Calculations for the substrate were performed in slabs of several unit cells in each direction. The N2 and NH3 adsorbates were attached to a central location at the Ga-lined surface.

The rate of chemical weathering of pyrite on the surface of Venus

NASA Technical Reports Server (NTRS)

Fegley, B., Jr.; Lodders, K.

1993-01-01

This abstract reports results of an experimental study of the chemical weathering of pyrite (FeS2) under Venus-like conditions. This work, which extends the earlier study by Fegley and Treiman, is part of a long range research program to experimentally measure the rates of thermochemical gas-solid reactions important in the atmospheric-lithospheric sulfur cycle on Venus. The objectives of this research are (1) to measure the kinetics of thermochemical gas-solid reactions responsible for both the production (e.g., anhydrite formation) and destruction (e.g., pyrrhotite oxidation) of sulfur-bearing minerals on the surface of Venus and (2) to incorporate these and other constraints into holistic models of the chemical interactions between the atmosphere and surface of Venus. Experiments were done with single crystal cubes of natural pyrite (Navajun, Logrono, Spain) that were cut and polished into slices of known weight and surface area. The slices were isothermally heated at atmospheric pressure in 99.99 percent CO2 (Coleman Instrument Grade) at either 412 C (685 K) or 465 C (738 K) for time periods up to 10 days. These two isotherms correspond to temperatures at about 6 km and 0 km altitude, respectively, on Venus. The reaction rate was determined by measuring the weight loss of the reacted slices after removal from the furnace. The reaction products were characterized by X-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy on the SEM.

Thermal decomposition of sewage sludge under N2, CO2 and air: Gas characterization and kinetic analysis.

PubMed

Hernández, Ana Belén; Okonta, Felix; Freeman, Ntuli

2017-07-01

Thermochemical valorisation processes that allow energy to be recovered from sewage sludge, such as pyrolysis and gasification, have demonstrated great potential as convenient alternatives to conventional sewage sludge disposal technologies. Moreover, these processes may benefit from CO 2 recycling. Today, the scaling up of these technologies requires an advanced knowledge of the reactivity of sewage sludge and the characteristics of the products, specific to the thermochemical process. In this study the behaviour of sewage sludge during thermochemical conversion, under different atmospheres (N 2 , CO 2 and air), was studied, using TGA-FTIR, in order to understand the effects of different atmospheric gases on the kinetics of degradation and on the gaseous products. The different steps observed during the solid degradation were related with the production of different gaseous compounds. A higher oxidative degree of the atmosphere surrounding the sample resulted in higher reaction rates and a shift of the degradation mechanisms to lower temperatures, especially for the mechanisms taking place at temperatures above 400 °C. Finally, a multiple first-order reaction model was proposed to compare the kinetic parameters obtained under different atmospheres. Overall, the highest activation energies were obtained for combustion. This work proves that CO 2 , an intermediate oxidative atmosphere between N 2 and air, results in an intermediate behaviour (intermediate peaks in the derivative thermogravimetric curves and intermediate activation energies) during the thermochemical decomposition of sewage sludge. Overall, it can be concluded that the kinetics of these different processes require a different approach for their scaling up and specific consideration of their characteristic reaction temperatures and rates should be evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lifecycle assessment of microalgae to biofuel: Comparison of thermochemical processing pathways

DOE PAGES

Bennion, Edward P.; Ginosar, Daniel M.; Moses, John; ...

2015-01-16

Microalgae are currently being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the impact of two different thermochemical conversion technologies on the microalgae to biofuel process through life cycle assessment. A system boundary of a “well to pump” (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimentalmore » and literature data and are representative of an industrial-scale microalgae to biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of -11.4 g CO 2-eq (MJ renewable diesel) -1. WTP biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO2 eq (MJ renewable diesel)-1. The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying requirements and combustion of co-products to improve system energetics. Discussion focuses on a detailed breakdown of the overall process energetics and GHGs, impact of modeling at laboratory- scale compared to industrial-scale, environmental impact sensitivity to engineering systems input parameters for future focused research and development and a comparison of results to literature.« less

Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO2 nuclear fuel

NASA Astrophysics Data System (ADS)

Piro, M. H. A.; Banfield, J.; Clarno, K. T.; Simunovic, S.; Besmann, T. M.; Lewis, B. J.; Thompson, W. T.

2013-10-01

Predictive capabilities for simulating irradiated nuclear fuel behavior are enhanced in the current work by coupling thermochemistry, isotopic evolution and heat transfer. Thermodynamic models that are incorporated into this framework not only predict the departure from stoichiometry of UO2, but also consider dissolved fission and activation products in the fluorite oxide phase, noble metal inclusions, secondary oxides including uranates, zirconates, molybdates and the gas phase. Thermochemical computations utilize the spatial and temporal evolution of the fission and activation product inventory in the pellet, which is typically neglected in nuclear fuel performance simulations. Isotopic computations encompass the depletion, decay and transmutation of more than 2000 isotopes that are calculated at every point in space and time. These computations take into consideration neutron flux depression and the increased production of fissile plutonium near the fuel pellet periphery (i.e., the so-called “rim effect”). Thermochemical and isotopic predictions are in very good agreement with reported experimental measurements of highly irradiated UO2 fuel with an average burnup of 102 GW d t(U)-1. Simulation results demonstrate that predictions are considerably enhanced when coupling thermochemical and isotopic computations in comparison to empirical correlations. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

Life cycle assessment of microalgae to biofuel: Thermochemical processing through hydrothermal liquefaction or pyrolysis

NASA Astrophysics Data System (ADS)

Bennion, Edward P.

Microalgae are currently being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the impact of two different thermochemical conversion technologies on the microalgae-to-biofuel process through life cycle assessment. A system boundary of a "well to pump" (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimental and literature data and are representative of an industrial-scale microalgae-to-biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of -11.4 g CO2 eq (MJ renewable diesel)-1. WTP biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO2 eq (MJ renewable diesel)-1. The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying requirements and combustion of co-products to improve system energetics. Discussion focuses on a detailed breakdown of the overall process energetics and GHGs, impact of modeling at laboratory-scale compared to industrial-scale, environmental impact sensitivity to engineering systems input parameters for future focused research and development, and a comparison of results to literature.

Thermo-chemical Ice Penetrator for Icy Moons

NASA Astrophysics Data System (ADS)

Arenberg, J. W.; Lee, G.; Harpole, G.; Zamel, J.; Sen, B.; Ross, F.; Retherford, K. D.

2016-12-01

The ability to place sensors or to take samples below the ice surface enables a wide variety of potential scientific investigations. Penetrating an ice cap can be accomplished via a mechanical drill, laser drill, kinetic impactor, or heated penetrator. This poster reports on the development of technology for the latter most option, namely a self-heated probe driven by an exothermic chemical reaction: a Thermo-chemical ice penetrator (TChIP). Our penetrator design employs a eutectic mix of alkali metals that produce an exothermic reaction upon contact with an icy surface. This reaction increases once the ice starts melting, so no external power is required. This technology is inspired by a classified Cold-War era program developed at Northrop Grumman for the US Navy. Terrestrial demonstration of this technology took place in the Arctic; however, this device cannot be considered high TRL for application at the icy moons of the solar system due to the environmental differences between Earth's Arctic and the icy moons. These differences demand a TChIP design specific to these cold, low mass, airless worlds. It is expected that this model of TChIP performance will be complex, incorporating all of the forces on the penetrator, gravity, the thermo-chemistry at the interface between penetrator and ice, and multi-phase heat and mass transport, and hydrodynamics. Our initial efforts are aimed at the development of a validated set of tools and simulations to predict the performance of the penetrator for both the environment found on these icy moons and for a terrestrial environment. The purpose of the inclusion of the terrestrial environment is to aid in model validation. Once developed and validated, our models will allow us to design penetrators for a specific scientific application on a specific body. This poster discusses the range of scientific investigations that are enabled by TChIP. We also introduce the development plan to advance TChIP to the point where it can be considered for infusion into a program.

Technology for a Thermo-chemical Ice Penetrator for Icy Moons

NASA Astrophysics Data System (ADS)

Arenberg, Jonathan; Harpole, George; Zamel, James; Sen, Bashwar; Lee, Greg; Ross, Floyd; Retherford, Kurt D.

2016-10-01

The ability to place sensors or to take samples below the ice surface enables a wide variety of potential scientific investigations. Penetrating an ice cap can be accomplished via a mechanical drill, laser drill, kinetic impactor, or heated penetrator. This poster reports on the development of technology for the latter most option, namely a self-heated probe driven by an exothermic chemical reaction: a Thermo-chemical ice penetrator (TChIP). Our penetrator design employs a eutectic mix of alkali metals that produce an exothermic reaction upon contact with an icy surface. This reaction increases once the ice starts melting, so no external power is required. This technology is inspired by a classified Cold-War era program developed at Northrop Grumman for the US Navy. Terrestrial demonstration of this technology took place in the Arctic; however, this device cannot be considered high TRL for application at the icy moons of the solar system due to the environmental differences between Earth's Arctic and the icy moons. These differences demand a TChIP design specific to these cold, low mass, airless worlds. It is expected that this model of TChIP performance will be complex, incorporating all of the forces on the penetrator, gravity, the thermo-chemistry at the interface between penetrator and ice, and multi-phase heat and mass transport, and hydrodynamics. Our initial efforts are aimed at the development of a validated set of tools and simulations to predict the performance of the penetrator for both the environment found on these icy moons and for a terrestrial environment. The purpose of the inclusion of the terrestrial environment is to aid in model validation. Once developed and validated, our models will allow us to design penetrators for a specific scientific application on a specific body. This poster discusses the range of scientific investigations that are enabled by TChIP. We also introduce the development plan to advance TChIP to the point where it can be considered for infusion into a program.

The equation of state of predominant detonation products

NASA Astrophysics Data System (ADS)

Zaug, Joseph; Crowhurst, Jonathan; Bastea, Sorin; Fried, Laurence

2009-06-01

The equation of state of detonation products, when incorporated into an experimentally grounded thermochemical reaction algorithm can be used to predict the performance of explosives. Here we report laser based Impulsive Stimulated Light Scattering measurements of the speed of sound from a variety of polar and nonpolar detonation product supercritical fluids and mixtures. The speed of sound data are used to improve the exponential-six potentials employed within the Cheetah thermochemical code. We will discuss the improvements made to Cheetah in terms of predictions vs. measured performance data for common polymer blended explosives. Accurately computing the chemistry that occurs from reacted binder materials is one important step forward in our efforts.

Thermochemical study of the system Fe-As-S

USGS Publications Warehouse

Barton, P.B.

1969-01-01

The results of Toulmin and Barton (1964) for the Fe-S system have been combined with a series of new measurements on As-bearing assemblages in the 500??-850??C temperature range to derive data on the free energies, enthalpies, and entropies of formation for arsenopyrite, loellingite, orpiment, realgar, FeAs, and Fe2As. The enthalpies and free energies of formation of orpiment and realgar are only approximately one-half as large as indicated in recent compilations of thermochemical data (Wagman et al., 1965). Data are also presented for the covariation of activity of S2(g) with temperature and composition of the sulfur-arsenic liquid. ?? 1969.

Solar thermochemical process interface study

NASA Technical Reports Server (NTRS)

1984-01-01

The design and analyses of a subsystem of a hydrogen production process are described. The process is based on solar driven thermochemical reactions. The subject subsystem receives sulfuric acid of 60% concentration at 100 C, 1 atm pressure. The acid is further concentrated, vaporized, and decomposed (at a rate of 122 g moles/sec H2SO4) into SO2, O2, and water. The produce stream is cooled to 100 C. Three subsystem options, each being driven by direct solar energy, were designed and analyzed. The results are compared with a prior study case in which solar energy was provided indirectly through a helium loop.

Process for the thermochemical production of hydrogen

DOEpatents

Norman, John H.; Russell, Jr., John L.; Porter, II, John T.; McCorkle, Kenneth H.; Roemer, Thomas S.; Sharp, Robert

1978-01-01

Hydrogen is thermochemically produced from water in a cycle wherein a first reaction produces hydrogen iodide and H.sub.2 SO.sub.4 by the reaction of iodine, sulfur dioxide and water under conditions which cause two distinct aqueous phases to be formed, i.e., a lighter sulfuric acid-bearing phase and a heavier hydrogen iodide-bearing phase. After separation of the two phases, the heavier phase containing most of the hydrogen iodide is treated, e.g., at a high temperature, to decompose the hydrogen iodide and recover hydrogen and iodine. The H.sub.2 SO.sub.4 is pyrolyzed to recover sulfur dioxide and produce oxygen.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1981-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermochemical generation of hydrogen and oxygen from water

DOEpatents

Robinson, Paul R.; Bamberger, Carlos E.

1982-01-01

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

NASA Astrophysics Data System (ADS)

Barmina, I.; Kolmickovs, A.; Valdmanis, R.; Vostrikovs, S.; Zake, M.

2018-05-01

Thermo-chemical conversion of microwave activated wheat straw mixtures with wood or peat pellets is studied experimentally with the aim to provide more effective application of wheat straw for heat energy production. Microwave pre-processing of straw pellets is used to provide a partial decomposition of the main constituents of straw and to activate the thermo-chemical conversion of wheat straw mixtures with wood or peat pellets. The experimental study includes complex measurements of the elemental composition of biomass pellets (wheat straw, wood, peat), DTG analysis of their thermal degradation, FTIR analysis of the composition of combustible volatiles entering the combustor, the flame temperature, the heat output of the device and composition of the products by comparing these characteristics for mixtures with unprocessed and mw pre-treated straw pellets. The results of experimental study confirm that mw pre-processing of straw activates the thermal decomposition of mixtures providing enhanced formation of combustible volatiles. This leads to improvement of the combustion conditions in the flame reaction zone, completing thus the combustion of volatiles, increasing the flame temperature, the heat output from the device, the produced heat energy per mass of burned mixture and decreasing at the same time the mass fraction of unburned volatiles in the products.

Thermal tests of a multi-tubular reactor for hydrogen production by using mixed ferrites thermochemical cycle

NASA Astrophysics Data System (ADS)

Gonzalez-Pardo, Aurelio; Denk, Thorsten; Vidal, Alfonso

2017-06-01

The SolH2 project is an INNPACTO initiative of the Spanish Ministry of Economy and Competitiveness, with the main goal to demonstrate the technological feasibility of solar thermochemical water splitting cycles as one of the most promising options to produce H2 from renewable sources in an emission-free way. A multi-tubular solar reactor was designed and build to evaluate a ferrite thermochemical cycle. At the end of this project, the ownership of this plant was transferred to CIEMAT. This paper reviews some additional tests with this pilot plant performed in the Plataforma Solar de Almería with the main goal to assess the thermal behavior of the reactor, evaluating the evolution of the temperatures inside the cavity and the relation between supplied power and reached temperatures. Previous experience with alumina tubes showed that they are very sensitive to temperature and flux gradients, what leads to elaborate an aiming strategy for the heliostat field to achieve a uniform distribution of the radiation inside the cavity. Additionally, the passing of clouds is a phenomenon that importantly affects all the CSP facilities by reducing their efficiency. The behavior of the reactor under these conditions has been studied.

Analysis of Efficiency of the Ship Propulsion System with Thermochemical Recuperation of Waste Heat

NASA Astrophysics Data System (ADS)

Cherednichenko, Oleksandr; Serbin, Serhiy

2018-03-01

One of the basic ways to reduce polluting emissions of ship power plants is application of innovative devices for on-board energy generation by means of secondary energy resources. The combined gas turbine and diesel engine plant with thermochemical recuperation of the heat of secondary energy resources has been considered. It is suggested to conduct the study with the help of mathematical modeling methods. The model takes into account basic physical correlations, material and thermal balances, phase equilibrium, and heat and mass transfer processes. The paper provides the results of mathematical modeling of the processes in a gas turbine and diesel engine power plant with thermochemical recuperation of the gas turbine exhaust gas heat by converting a hydrocarbon fuel. In such a plant, it is possible to reduce the specific fuel consumption of the diesel engine by 20%. The waste heat potential in a gas turbine can provide efficient hydrocarbon fuel conversion at the ratio of powers of the diesel and gas turbine engines being up to 6. When the diesel engine and gas turbine operate simultaneously with the use of the LNG vapor conversion products, the efficiency coefficient of the plant increases by 4-5%.

Thermochemical Compatibility and Oxidation Resistance of Advanced LWR Fuel Cladding

DOE PAGES

Besmann, T. M.; Yamamoto, Y.; Unocic, K. A.

2016-06-21

We assessed the thermochemical compatibility of potential replacement cladding materials for zirconium alloys in light water reactors. Considered were FeCrAl steel (similar to Kanthal APMT), Nb-1%Zr (similar to PWC-11), and a hybrid SiC-composite with a metallic barrier layer. The niobium alloy was also seen as requiring an oxidation protective layer, and a diffusion silicide was investigated. Metallic barrier layers for the SiC-composite reviewed included a FeCrAl alloy, Nb-1%Zr, and chromium. Thermochemical calculations were performed to determine oxidation behavior of the materials in steam, and for hybrid SiC-composites possible interactions between the metallic layer and SiC. Additionally, experimental exposures of SiC-alloymore » reaction couples at 673K, 1073K, and 1273K for 168 h in an inert atmosphere were made and microanalysis performed. Whereas all materials were determined to oxidize under higher oxygen partial pressures in the steam environment, these varied by material with expected protective oxides forming. Finally, the computed and experimental results indicate the formation of liquid phase eutectic in the FeCrAl-SiC system at the higher temperatures.« less

Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes.

PubMed

Virmond, Elaine; De Sena, Rennio F; Albrecht, Waldir; Althoff, Christine A; Moreira, Regina F P M; José, Humberto J

2012-10-01

In the present work, selected agroindustrial solid residues from Brazil - biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk - were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJkg(-1) to 29.14 MJkg(-1), on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

PubMed

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE PAGES

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing; ...

2017-07-05

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benincosa, William; Siriwardane, Ranjani; Tian, Hanjing

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLCmore » reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4, from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.« less

Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

PubMed

Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

2016-05-15

Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability. Copyright © 2016 Elsevier Inc. All rights reserved.

Modelling the combustion of charcoal in a model blast furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Shiozawa, Tomo; Yu, Aibing; Austin, Peter

2013-07-01

The pulverized charcoal (PCH) combustion in ironmaking blast furnaces is abstracting remarkable attention due to various benefits such as lowering CO2 emission. In this study, a three-dimensional CFD model is used to simulate the flow and thermo-chemical behaviours in this process. The model is validated against the experimental results from a pilot-scale combustion test rig for a range of conditions. The typical flow and thermo-chemical phenomena is simulated. The effect of charcoal type, i.e. VM content is examined, showing that the burnout increases with VM content in a linear relationship. This model provides an effective way for designing and optimizing PCH operation in blast furnace practice.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nexant, Inc., San Francisco, California

The first section (Task 1) of this report by Nexant includes a survey and screening of various acid gas removal processes in order to evaluate their capability to meet the specific design requirements for thermochemical ethanol synthesis in NREL's thermochemical ethanol design report (Phillips et al. 2007, NREL/TP-510-41168). MDEA and selexol were short-listed as the most promising acid-gas removal agents based on work described in Task 1. The second report section (Task 2) describes a detailed design of an MDEA (methyl diethanol amine) based acid gas removal system for removing CO2 and H2S from biomass-derived syngas. Only MDEA was chosenmore » for detailed study because of the available resources.« less

Estimating Equivalency of Explosives Through A Thermochemical Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maienschein, J L

2002-07-08

The Cheetah thermochemical computer code provides an accurate method for estimating the TNT equivalency of any explosive, evaluated either with respect to peak pressure or the quasi-static pressure at long time in a confined volume. Cheetah calculates the detonation energy and heat of combustion for virtually any explosive (pure or formulation). Comparing the detonation energy for an explosive with that of TNT allows estimation of the TNT equivalency with respect to peak pressure, while comparison of the heat of combustion allows estimation of TNT equivalency with respect to quasi-static pressure. We discuss the methodology, present results for many explosives, andmore » show comparisons with equivalency data from other sources.« less

A thermochemical model of radiation damage and annealing applied to GaAs solar cells

NASA Technical Reports Server (NTRS)

Conway, E. J.; Walker, G. H.; Heinbockel, J. H.

1981-01-01

Calculations of the equilibrium conditions for continuous radiation damage and thermal annealing are reported. The calculations are based on a thermochemical model developed to analyze the incorporation of point imperfections in GaAs, and modified by introducing the radiation to produce native lattice defects rather than high-temperature and arsenic atmospheric pressure. The concentration of a set of defects, including vacancies, divacancies, and impurity vacancy complexes, are calculated as a function of temperature. Minority carrier lifetimes, short circuit current, and efficiency are deduced for a range of equilibrium temperatures. The results indicate that GaAs solar cells could have a mission life which is not greatly limited by radiation damage.

A theoretical study of the structure and thermochemical properties of alkali metal fluoroplumbates MPbF3.

PubMed

Boltalin, A I; Korenev, Yu M; Sipachev, V A

2007-07-19

Molecular constants of MPbF3 (M=Li, Na, K, Rb, and Cs) were calculated theoretically at the MP2(full) and B3LYP levels with the SDD (Pb, K, Rb, and Cs) and cc-aug-pVQZ (F, Li, and Na) basis sets to determine the thermochemical characteristics of the substances. Satisfactory agreement with experiment was obtained, including the unexpected nonmonotonic dependence of substance dissociation energies on the alkali metal atomic number. The bond lengths of the theoretical CsPbF3 model were substantially elongated compared with experimental estimates, likely because of errors in both theoretical calculations and electron diffraction data processing.

Particle kinetic simulation of high altitude hypervelocity flight

NASA Technical Reports Server (NTRS)

Heinemann, Klaus; Boyd, Iain D.; Haas, Brian L.

1993-01-01

In this grant period, the focus has been on the effects of thermo-chemical nonequilibrium in low-density gases, and on interactions between such gases and solid surfaces. Such conditions apply to hypersonic flows of re-entry vehicles, and to the expansion plumes of small rockets. Due to the nonequilibrium nature of these flows, a particle approach has been adopted. The method continues to undergo refinement and application to typical flows of interest. A number of studies have been performed for flows in thermo-chemical nonequilibrium. The effects of vibrational nonequilibrium on the rate of dissociation were studied for diatomic nitrogen. It was found that a new model reproduced the nonequilibrium behavior observed experimentally.

Thermochemical characterization of pigeon pea stalk for its efficient utilization as an energy source

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katyal, S.K.; Iyer, P.V.R.

2000-05-01

Pigeon pea stalk is a widely available biomass species in India. In this article the potential use of pigeon pea stalk as a fuel source through thermochemical conversion methods such as combustion, gasification, and pyrolysis has been investigated through experimentation using a thermogravimetric analyzer and pilot-plant-scale equipment. It has been proposed that pigeon pea stalks can be effectively utilized in two ways. The first is to pyrolyze the material to produce value-added products such as char, tar, and fuel gas. The second alternative is to partially pyrolyze the material to remove tar-forming volatiles, followed by gasification of reactive char tomore » generate producer gas.« less

Thermochemical generation of hydrogen and oxygen from water. [NaMnO/sub 2/ and TiO/sub 2/

DOEpatents

Robinson, P.R.; Bamberger, C.E.

1980-02-08

A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO/sub 2/) and titanium dioxide (TiO/sub 2/) to form sodium titanate (Na/sub 2/TiO/sub 3/), manganese (II) titanate (MnTiO/sub 3/) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

Hydrogen as an energy medium

NASA Technical Reports Server (NTRS)

Cox, K. E.

1976-01-01

Coal, though abundant in certain geographical locations of the USA poses environmental problems associated with its mining and combustion. Also, nuclear fission energy appears to have problems regarding safety and radioactive waste disposal that are as yet unresolved. The paper discusses hydrogen use and market projection along with energy sources for hydrogen production. Particular attention is given to hydrogen production technology as related to electrolysis and thermochemical water decomposition. Economics of hydrogen will ultimately be determined by the price and availability of future energy carriers such as electricity and synthetic natural gas. Thermochemical methods of hydrogen production appear to offer promise largely in the efficiency of energy conversion and in capital costs over electrolytic methods.

Radiation Transport Around Axisymmetric Blunt Body Vehicles Using a Modified Differential Approximation

NASA Technical Reports Server (NTRS)

Hartung, Lin C.; Hassan, H. A.

1992-01-01

A moment method for computing 3-D radiative transport is applied to axisymmetric flows in thermochemical nonequilibrium. Such flows are representative of proposed aerobrake missions. The method uses the P-1 approximation to reduce the governing system of integro-di erential equations to a coupled set of partial di erential equations. A numerical solution method for these equations given actual variations of the radiation properties in thermochemical nonequilibrium blunt body flows is developed. Initial results from the method are shown and compared to tangent slab calculations. The agreement between the transport methods is found to be about 10 percent in the stagnation region, with the difference increasing along the flank of the vehicle.

Lance Wheeler | NREL

Science.gov Websites

solution-phase phenomena of nanomaterials Switchable photovoltaics Solar thermochemical fuel production methylammonium lead halide perovskites during thermal processing from solution," Energy & Environmental

The life story of hydrogen peroxide II: a periodic pH and thermochemical drive for the RNA world

PubMed Central

Ball, Rowena; Brindley, John

2015-01-01

It is now accepted that primordial non-cellular RNA communities must have been subject to a periodic drive in order to replicate and prosper. We have proposed the oxidation of thiosulfate by hydrogen peroxide as this drive. This reaction system behaves as (i) a thermochemical and (ii) a pH oscillator, and in this work, we unify (i) and (ii) for the first time. We report thermally self-consistent, dynamical simulations in which the system transitions smoothly from nearly isothermal pH to fully developed thermo-pH oscillatory regimes. We use this oscillator to drive simulated replication of a 39-bp RNA species. Production of replicated duplex under thermo-pH drive was significantly enhanced compared with that under purely thermochemical drive, effectively allowing longer strands to replicate. Longer strands are fitter, with more potential to evolve enzyme activity and resist degradation. We affirm that concern over the alleged toxicity of hydrogen peroxide to life is largely misplaced in the current context, we survey its occurrence in the solar system to motivate its inclusion as a biosignature in the search for life on other worlds and highlight that pH oscillations in a spatially extended, bounded system manifest as the fundamental driving force of life: a proton gradient. PMID:26202683

Investigation of La xSr 1-xCo yM 1-yO 3-δ (M = Mn Fe) perovskite materials as thermochemical energy storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babiniec, Sean Michael; Coker, Eric Nicholas; Miller, James E.

2015-06-23

Materials in the La xSr 1–xCo yMn 1–yO 3–δ (LSCM) and La xSr 1–xCo yFe 1–yO 3–δ (LSCF) families are candidates for high-temperature thermochemical energy storage due to their facility for cyclic endothermic reduction and exothermic oxidation. A set of 16 LSCM and 21 LSCF compositions were synthesized by a modified Pechini method and characterized by powder X-ray diffraction and thermogravimetric analysis. All materials were found to be various symmetries of the perovskite phase. LSCM was indexed as tetragonal, cubic, rhombohedral, or orthorhombic as a function of increased lanthanum content. For LSCF, compositions containing low lanthanum content were indexed asmore » cubic while materials with high lanthanum content were indexed as rhombohedral. An initial screening of redox activity was completed by thermogravimetric analysis for each composition. The top three compositions with the greatest recoverable redox capacity for each family were further characterized in equilibrium thermogravimetric experiments over a range of temperatures and oxygen partial pressures. As a result, these equilibrium experiments allowed the extraction of thermodynamic parameters for LSCM and LSCF compositions operated in thermochemical energy storage conditions.« less

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

PubMed Central

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-01-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134–57.500 gr ethanol kg−1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis. PMID:27291594

Climate Impact and Economic Feasibility of Solar Thermochemical Jet Fuel Production.

PubMed

Falter, Christoph; Batteiger, Valentin; Sizmann, Andreas

2016-01-05

Solar thermochemistry presents a promising option for the efficient conversion of H2O and CO2 into liquid hydrocarbon fuels using concentrated solar energy. To explore the potential of this fuel production pathway, the climate impact and economic performance are analyzed. Key drivers for the economic and ecological performance are thermochemical energy conversion efficiency, the level of solar irradiation, operation and maintenance, and the initial investment in the fuel production plant. For the baseline case of a solar tower concentrator with CO2 capture from air, jet fuel production costs of 2.23 €/L and life cycle greenhouse gas (LC GHG) emissions of 0.49 kgCO2-equiv/L are estimated. Capturing CO2 from a natural gas combined cycle power plant instead of the air reduces the production costs by 15% but leads to LC GHG emissions higher than that of conventional jet fuel. Favorable assumptions for all involved process steps (30% thermochemical energy conversion efficiency, 3000 kWh/(m(2) a) solar irradiation, low CO2 and heliostat costs) result in jet fuel production costs of 1.28 €/L at LC GHG emissions close to zero. Even lower production costs may be achieved if the commercial value of oxygen as a byproduct is considered.

Development and application of computational aerothermodynamics flowfield computer codes

NASA Technical Reports Server (NTRS)

Venkatapathy, Ethiraj

1994-01-01

Research was performed in the area of computational modeling and application of hypersonic, high-enthalpy, thermo-chemical nonequilibrium flow (Aerothermodynamics) problems. A number of computational fluid dynamic (CFD) codes were developed and applied to simulate high altitude rocket-plume, the Aeroassist Flight Experiment (AFE), hypersonic base flow for planetary probes, the single expansion ramp model (SERN) connected with the National Aerospace Plane, hypersonic drag devices, hypersonic ramp flows, ballistic range models, shock tunnel facility nozzles, transient and steady flows in the shock tunnel facility, arc-jet flows, thermochemical nonequilibrium flows around simple and complex bodies, axisymmetric ionized flows of interest to re-entry, unsteady shock induced combustion phenomena, high enthalpy pulsed facility simulations, and unsteady shock boundary layer interactions in shock tunnels. Computational modeling involved developing appropriate numerical schemes for the flows on interest and developing, applying, and validating appropriate thermochemical processes. As part of improving the accuracy of the numerical predictions, adaptive grid algorithms were explored, and a user-friendly, self-adaptive code (SAGE) was developed. Aerothermodynamic flows of interest included energy transfer due to strong radiation, and a significant level of effort was spent in developing computational codes for calculating radiation and radiation modeling. In addition, computational tools were developed and applied to predict the radiative heat flux and spectra that reach the model surface.

Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

NASA Astrophysics Data System (ADS)

Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

2016-06-01

Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134-57.500 gr ethanol kg-1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis.

Effect of various types of thermochemical processing of sewage sludges on phosphorus speciation, solubility, and fertilization performance.

PubMed

Steckenmesser, Daniel; Vogel, Christian; Adam, Christian; Steffens, Diedrich

2017-04-01

Sewage sludge has one of the highest phosphorus (P) recovery potentials of all waste materials. Therefore, P-recycling from sewage sludge could contribute to closing the P-cycle. Recently, various thermal processes for P-recovery have been developed, but there is still a demand for information on the effect of different process parameters (e.g. additives and temperature) on P-speciation and especially on the fertilization performance. In the present study, two common methods (low-temperature conversion at 400-500°C and thermochemical treatment at 950°C) were investigated and combined to produce highly bioavailable P-fertilizers from two different types of sewage sludge based on chemical phosphorus precipitation (Chem-P) and enhanced biological phosphorus removal (Bio-P). The results of P-fractionation, X-ray diffraction analysis, and pot experiments with maize showed that Bio-P sludges attain high P-plant-availability after treatment at low temperatures (400°C). In contrast, Chem-P sludges can adequately be treated at higher temperatures under reductive conditions with sodium additives to form highly bioavailable calcium-sodium-phosphate. Additionally, also highly heavy-metal contaminated sludges can be thermochemically treated at high temperatures to achieve the legal requirements for fertilizers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics and mechanism of solid decompositions — From basic discoveries by atomic absorption spectrometry and quadrupole mass spectroscopy to thorough thermogravimetric analysis

NASA Astrophysics Data System (ADS)

L'vov, Boris V.

2008-02-01

This paper sums up the evolution of thermochemical approach to the interpretation of solid decompositions for the past 25 years. This period includes two stages related to decomposition studies by different techniques: by ET AAS and QMS in 1981-2001 and by TG in 2002-2007. As a result of ET AAS and QMS investigations, the method for determination of absolute rates of solid decompositions was developed and the mechanism of decompositions through the congruent dissociative vaporization was discovered. On this basis, in the period from 1997 to 2001, the decomposition mechanisms of several classes of reactants were interpreted and some unusual effects observed in TA were explained. However, the thermochemical approach has not received any support by other TA researchers. One of the potential reasons of this distrust was the unreliability of the E values measured by the traditional Arrhenius plot method. The theoretical analysis and comparison of metrological features of different methods used in the determinations of thermochemical quantities permitted to conclude that in comparison with the Arrhenius plot and second-law methods, the third-law method is to be very much preferred. However, this method cannot be used in the kinetic studies by the Arrhenius approach because its use suggests the measuring of the equilibrium pressures of decomposition products. On the contrary, the method of absolute rates is ideally suitable for this purpose. As a result of much higher precision of the third-law method, some quantitative conclusions that follow from the theory were confirmed, and several new effects, which were invisible in the framework of the Arrhenius approach, have been revealed. In spite of great progress reached in the development of reliable methodology, based on the third-law method, the thermochemical approach remains unclaimed as before.

Biomass thermochemical gasification: Experimental studies and modeling

NASA Astrophysics Data System (ADS)

Kumar, Ajay

The overall goals of this research were to study the biomass thermochemical gasification using experimental and modeling techniques, and to evaluate the cost of industrial gas production and combined heat and power generation. This dissertation includes an extensive review of progresses in biomass thermochemical gasification. Product gases from biomass gasification can be converted to biopower, biofuels and chemicals. However, for its viable commercial applications, the study summarizes the technical challenges in the gasification and downstream processing of product gas. Corn stover and dried distillers grains with solubles (DDGS), a non-fermentable byproduct of ethanol production, were used as the biomass feedstocks. One of the objectives was to determine selected physical and chemical properties of corn stover related to thermochemical conversion. The parameters of the reaction kinetics for weight loss were obtained. The next objective was to investigate the effects of temperature, steam to biomass ratio and equivalence ratio on gas composition and efficiencies. DDGS gasification was performed on a lab-scale fluidized-bed gasifier with steam and air as fluidizing and oxidizing agents. Increasing the temperature resulted in increases in hydrogen and methane contents and efficiencies. A model was developed to simulate the performance of a lab-scale gasifier using Aspen Plus(TM) software. Mass balance, energy balance and minimization of Gibbs free energy were applied for the gasification to determine the product gas composition. The final objective was to optimize the process by maximizing the net energy efficiency, and to estimate the cost of industrial gas, and combined heat and power (CHP) at a biomass feedrate of 2000 kg/h. The selling price of gas was estimated to be 11.49/GJ for corn stover, and 13.08/GJ for DDGS. For CHP generation, the electrical and net efficiencies were 37 and 86%, respectively for corn stover, and 34 and 78%, respectively for DDGS. For corn stover, the selling price of electricity was 0.1351/kWh. For DDGS, the selling price of electricity was 0.1287/kWh.

Third millenium ideal gas and condensed phase thermochemical database for combustion (with update from active thermochemical tables).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burcat, A.; Ruscic, B.; Chemistry

2005-07-29

The thermochemical database of species involved in combustion processes is and has been available for free use for over 25 years. It was first published in print in 1984, approximately 8 years after it was first assembled, and contained 215 species at the time. This is the 7th printed edition and most likely will be the last one in print in the present format, which involves substantial manual labor. The database currently contains more than 1300 species, specifically organic molecules and radicals, but also inorganic species connected to combustion and air pollution. Since 1991 this database is freely available onmore » the internet, at the Technion-IIT ftp server, and it is continuously expanded and corrected. The database is mirrored daily at an official mirror site, and at random at about a dozen unofficial mirror and 'finger' sites. The present edition contains numerous corrections and many recalculations of data of provisory type by the G3//B3LYP method, a high-accuracy composite ab initio calculation. About 300 species are newly calculated and are not yet published elsewhere. In anticipation of the full coupling, which is under development, the database started incorporating the available (as yet unpublished) values from Active Thermochemical Tables. The electronic version now also contains an XML file of the main database to allow transfer to other formats and ease finding specific information of interest. The database is used by scientists, educators, engineers and students at all levels, dealing primarily with combustion and air pollution, jet engines, rocket propulsion, fireworks, but also by researchers involved in upper atmosphere kinetics, astrophysics, abrasion metallurgy, etc. This introductory article contains explanations of the database and the means to use it, its sources, ways of calculation, and assessments of the accuracy of data.« less

Coupled thermo-chemical boundary conditions in double-diffusive geodynamo models at arbitrary Lewis numbers.

NASA Astrophysics Data System (ADS)

Bouffard, M.

2016-12-01

Convection in the Earth's outer core is driven by the combination of two buoyancy sources: a thermal source directly related to the Earth's secular cooling, the release of latent heat and possibly the heat generated by radioactive decay, and a compositional source due to the crystallization of the growing inner core which releases light elements into the liquid outer core. The dynamics of fusion/crystallization being dependent on the heat flux distribution, the thermochemical boundary conditions are coupled at the inner core boundary which may affect the dynamo in various ways, particularly if heterogeneous conditions are imposed at one boundary. In addition, the thermal and compositional molecular diffusivities differ by three orders of magnitude. This can produce significant differences in the convective dynamics compared to pure thermal or compositional convection due to the potential occurence of double-diffusive phenomena. Traditionally, temperature and composition have been combined into one single variable called codensity under the assumption that turbulence mixes all physical properties at an "eddy-diffusion" rate. This description does not allow for a proper treatment of the thermochemical coupling and is certainly incorrect within stratified layers in which double-diffusive phenomena can be expected. For a more general and rigorous approach, two distinct transport equations should therefore be solved for temperature and composition. However, the weak compositional diffusivity is technically difficult to handle in current geodynamo codes and requires the use of a semi-Lagrangian description to minimize numerical diffusion. We implemented a "particle-in-cell" method into a geodynamo code to properly describe the compositional field. The code is suitable for High Parallel Computing architectures and was successfully tested on two benchmarks. Following the work by Aubert et al. (2008) we use this new tool to perform dynamo simulations including thermochemical coupling at the inner core boundary as well as exploration of the infinite Lewis number limit to study the effect of a heterogeneous core mantle boundary heat flow on the inner core growth.

Thermodynamic Analysis of the Use a Chemical Heat Pump to Link a Supercritical Water-Cooled Nuclear Reactor and a Thermochemical Water-Splitting Cycle for Hydrogen Production

NASA Astrophysics Data System (ADS)

Granovskii, Mikhail; Dincer, Ibrahim; Rosen, Marc A.; Pioro, Igor

Increases in the power generation efficiency of nuclear power plants (NPPs) are mainly limited by the permissible temperatures in nuclear reactors and the corresponding temperatures and pressures of the coolants in reactors. Coolant parameters are limited by the corrosion rates of materials and nuclear-reactor safety constraints. The advanced construction materials for the next generation of CANDU reactors, which employ supercritical water (SCW) as a coolant and heat carrier, permit improved “steam” parameters (outlet temperatures up to 625°C and pressures of about 25 MPa). An increase in the temperature of steam allows it to be utilized in thermochemical water splitting cycles to produce hydrogen. These methods are considered by many to be among the most efficient ways to produce hydrogen from water and to have advantages over traditional low-temperature water electrolysis. However, even lower temperature water splitting cycles (Cu-Cl, UT-3, etc.) require an intensive heat supply at temperatures higher than 550-600°C. A sufficient increase in the heat transfer from the nuclear reactor to a thermochemical water splitting cycle, without jeopardizing nuclear reactor safety, might be effectively achieved by application of a heat pump, which increases the temperature of the heat supplied by virtue of a cyclic process driven by mechanical or electrical work. Here, a high-temperature chemical heat pump, which employs the reversible catalytic methane conversion reaction, is proposed. The reaction shift from exothermic to endothermic and back is achieved by a change of the steam concentration in the reaction mixture. This heat pump, coupled with the second steam cycle of a SCW nuclear power generation plant on one side and a thermochemical water splitting cycle on the other, increases the temperature of the “nuclear” heat and, consequently, the intensity of heat transfer into the water splitting cycle. A comparative preliminary thermodynamic analysis is conducted of the combined system comprising a SCW nuclear power generation plant and a chemical heat pump, which provides high-temperature heat to a thermochemical water splitting cycle for hydrogen production. It is concluded that the proposed chemical heat pump permits the utilization efficiency of nuclear energy to be improved by at least 2% without jeopardizing nuclear reactor safety. Based on this analysis, further research appears to be merited on the proposed advanced design of a nuclear power generation plant combined with a chemical heat pump, and implementation in appropriate applications seems worthwhile.

Thermal Storage Applications Workshop. Volume 2: Contributed Papers

NASA Technical Reports Server (NTRS)

1979-01-01

The solar thermal and the thermal and thermochemical energy storage programs are described as well as the technology requirements for both external (electrical) and internal (thermal, chemical) modes for energy storage in solar power plants. Specific technical issues addressed include thermal storage criteria for solar power plants interfacing with utility systems; optimal dispatch of storage for solar plants in a conventional electric grid; thermal storage/temperature tradeoffs for solar total energy systems; the value of energy storage for direct-replacement solar thermal power plants; systems analysis of storage in specific solar thermal power applications; the value of seasonal storage of solar energy; criteria for selection of the thermal storage system for a 10 MW(2) solar power plant; and the need for specific requirements by storage system development teams.

Catalytic Deoxygenation of Biomass Pyrolysis Vapors to Improve Bio-oil Stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dayton, David C.

2016-12-22

The President’s Advanced Energy Initiative called for a change in the way Americans fuel their vehicles to promote improved energy security. Increasing biofuels production from domestic lignocellulosic resources requires advanced technology development to achieve the aggressive targets set forth to reduce motor gasoline consumption by 20% in ten years (by 2017). The U.S. Department of Energy (USDOE) Office of the Biomass Program (currently Bioenergy Technologies Office) is actively funding research and development in both biochemical and thermochemical conversion technologies to accelerate the deployment of biofuels technologies in the near future to meet the goals of the Advanced Energy Initiative. Thermochemicalmore » conversion technology options include both gasification and pyrolysis to enable the developing lignocellulosic biorefineries and maximize biomass resource utilization for production of biofuels.« less

Detonation Velocity Calculations of Explosives with Slowly-Burning Constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1997-07-01

The thermochemical code Equilbrium CHEETAH has been modified to allow partial reaction of constituents and partial flow of heat. Solid or liquid reactants are described by Einstein oscillators, whose temperatures can be changed to allow heat transfer. Hydroxy-terminated-poly-budadiene, mixed with RDX or HMX, does not react, as shown by the effect on the calculated detonation velocity. Aluminum and ammonium perchlorate in composites also do not react. Only partial heat flow also takes place in the unreacted materials. These results show that the usual assumption of total burn in a thermochemical code is probably incorrect, at least in the sonic reaction zone that drives the detonation velocity. A kinetic code would be the logical extension of this work.

The development of an explicit thermochemical nonequilibrium algorithm and its application to compute three dimensional AFE flowfields

NASA Technical Reports Server (NTRS)

Palmer, Grant

1989-01-01

This study presents a three-dimensional explicit, finite-difference, shock-capturing numerical algorithm applied to viscous hypersonic flows in thermochemical nonequilibrium. The algorithm employs a two-temperature physical model. Equations governing the finite-rate chemical reactions are fully-coupled to the gas dynamic equations using a novel coupling technique. The new coupling method maintains stability in the explicit, finite-rate formulation while allowing relatively large global time steps. The code uses flux-vector accuracy. Comparisons with experimental data and other numerical computations verify the accuracy of the present method. The code is used to compute the three-dimensional flowfield over the Aeroassist Flight Experiment (AFE) vehicle at one of its trajectory points.

Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

PubMed Central

Haussener, Sophia; Steinfeld, Aldo

2012-01-01

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium. PMID:28817039

Thermochemical analysis of intermolecular interactions between N-acetylglycine and polyols in aqueous solutions

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2017-05-01

The integral enthalpies of dissolution Δsol H m for N-acetylglycine in aqueous solutions of glycerol, ethylene glycol and 1,2-propylene glycol are measured via solution calorimetry. The standard enthalpies of dissolution (Δsol H 0) and transfer (Δtr H 0) for N-acetylglycine from water to aqueous solutions of polyhydric alcohols are calculated from experimental data. Positive values of enthalpy coefficients of pair interactions h xy for amino acids and polyol molecules are calculated using the McMillan-Mayer theory. The results are discussed using an approach for evaluating different types of interactions in ternary systems and the effect the structural features of interacting biomolecules have on the thermochemical characteristics of N-acetylglycine dissolution.

Thermo-Chemical Convection in Europa's Icy Shell with Salinity

NASA Technical Reports Server (NTRS)

Han, L.; Showman, A. P.

2005-01-01

Europa's icy surface displays numerous pits, uplifts, and chaos terrains that have been suggested to result from solid-state thermal convection in the ice shell, perhaps aided by partial melting. However, numerical simulations of thermal convection show that plumes have insufficient buoyancy to produce surface deformation. Here we present numerical simulations of thermochemical convection to test the hypothesis that convection with salinity can produce Europa's pits and domes. Our simulations show that domes (200-300 m) and pits (300-400 m) comparable to the observations can be produced in an ice shell of 15 km thick with 5-10% compositional density variation if the maximum viscosity is less than 10(exp 18) Pa sec. Additional information is included in the original extended abstract.

Thermochemical production of hydrogen

DOEpatents

Dreyfuss, Robert M.

1976-07-13

A thermochemical reaction cycle for the generation of hydrogen from water comprising the following sequence of reactions wherein M represents a metal and Z represents a metalloid selected from the arsenic-antimony-bismuth and selenium-tellurium subgroups of the periodic system: 2MO + Z + SO.sub.2 .fwdarw. MZ + MSO.sub.4 (1) mz + h.sub.2 so.sub.4 .fwdarw. mso.sub.4 + h.sub.2 z (2) 2mso.sub.4 .fwdarw. 2mo + so.sub.2 + so.sub.3 + 1/20.sub.2 (3) h.sub.2 z .fwdarw. z + h.sub.2 (4) h.sub.2 o + so.sub.3 .fwdarw. h.sub.2 so.sub.4 (5) the net reaction is the decomposition of water into hydrogen and oxygen.

Method for thermochemical decomposition of water

DOEpatents

Abraham, Bernard M.; Schreiner, Felix

1977-01-11

Water is thermochemically decomposed to produce hydrogen by the following sequence of reactions: KI, NH.sub.3, CO.sub. 2 and water in an organic solvent such as ethyl or propyl alcohol are reacted to produce KHCO 3 and NH.sub.4 I. The KHCO.sub.3 is thermally decomposed to K.sub.2 CO.sub.3, H.sub.2 O and CO.sub.2, while the NH.sub.4 I is reacted with Hg to produce HgI.sub.2, NH.sub.3 and H.sub.2. The K.sub.2 CO.sub.3 obtained by calcining KHCO.sub.3 is then reacted with HgI.sub.2 to produce Hg, KI, CO and O.sub.2. All products of the reaction are recycled except hydrogen and oxygen.

Soot and Spectral Radiation Modeling in ECN Spray A and in Engines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haworth, Daniel C; Ferreyro-Fernandez, Sebastian; Paul, Chandan

The amount of soot formed in a turbulent combustion system is determined by a complex system of coupled nonlinear chemical and physical processes. Different physical subprocesses can dominate, depending on the hydrodynamic and thermochemical environments. Similarly, the relative importance of reabsorption, spectral radiation properties, and molecular gas radiation versus soot radiation varies with thermochemical conditions, and in ways that are difficult to predict for the highly nonhomogeneous in-cylinder mixtures in engines. Here it is shown that transport and mixing play relatively more important roles as rate-determining processes in soot formation at engine-relevant conditions. It is also shown that molecular gasmore » radiation and spectral radiation properties are important for engine-relevant conditions.« less

A thermochemical explanation for the stability of NaCl3 and NaCl7

NASA Astrophysics Data System (ADS)

Fernandes de Farias, Robson

2017-03-01

Thermodynamically stable cubic and orthorhombic NaCl3 as well as NaCl7 have been synthesized (Zhang et al., 2013). In the present work, a thermochemical explanation for the stability of such unusual sodium chlorides is provided, based on lattice energy values. Using the Glasser-Jenkins generalized equation (Glasser and Jenkins, 2000) lattice energies (kJ mol-1) of -162.5, -168.9 and -113.1 are calculated for Pm3n NaCl3, Pnma NaCl3 and NaCl7, respectively. It is postulated that any NaxCly compound could be synthesized, if the ionic character of the Nasbnd Cl bond in the prepared compound remains around 80%, and the sodium charge below unit.

Energy Conversion and Storage Program

NASA Astrophysics Data System (ADS)

Cairns, E. J.

1993-06-01

This report is the 1992 annual progress report for the Energy Conversion and Storage Program, a part of the Energy and Environment Division of the Lawrence Berkeley Laboratory. Work described falls into three broad areas: electrochemistry; chemical applications; and materials applications. The Energy Conversion and Storage Program applies principles of chemistry and materials science to solve problems in several areas: (1) production of new synthetic fuels, (2) development of high-performance rechargeable batteries and fuel cells, (3) development of advanced thermochemical processes for energy conversion, (4) characterization of complex chemical processes and chemical species, and (5) study and application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Chemical applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing product and waste streams from synfuel plants, coal gasifiers, and biomass conversion processes. Materials applications research includes evaluation of the properties of advanced materials, as well as development of novel preparation techniques. For example, techniques such as sputtering, laser ablation, and poised laser deposition are being used to produce high-temperature superconducting films.

Thermal/Pyrolysis Gas Flow Analysis of Carbon Phenolic Material

NASA Technical Reports Server (NTRS)

Clayton, J. Louie

2001-01-01

Provided in this study are predicted in-depth temperature and pyrolysis gas pressure distributions for carbon phenolic materials that are externally heated with a laser source. Governing equations, numerical techniques and comparisons to measured temperature data are also presented. Surface thermochemical conditions were determined using the Aerotherm Chemical Equilibrium (ACE) program. Surface heating simulation used facility calibrated radiative and convective flux levels. Temperatures and pyrolysis gas pressures are predicted using an upgraded form of the SINDA/CMA program that was developed by NASA during the Solid Propulsion Integrity Program (SPIP). Multispecie mass balance, tracking of condensable vapors, high heat rate kinetics, real gas compressibility and reduced mixture viscosity's have been added to the algorithm. In general, surface and in-depth temperature comparisons are very good. Specie partial pressures calculations show that a saturated water-vapor mixture is the main contributor to peak in-depth total pressure. Further, for most of the cases studied, the water-vapor mixture is driven near the critical point and is believed to significantly increase the local heat capacity of the composite material. This phenomenon if not accounted for in analysis models may lead to an over prediction in temperature response in charring regions of the material.

Microreactor System Design for a NASA In Situ Propellant Production Plant on Mars

NASA Technical Reports Server (NTRS)

TeGrotenhuis, W. E.; Wegeng, R. S.; Vanderwiel, D. P.; Whyatt, G. A.; Viswanathan, V. V.; Schielke, K. P.; Sanders, G. B.; Peters, T. A.; Nicholson, Leonard S. (Technical Monitor)

2000-01-01

The NASA In Situ Resource Utilization (ISRU) program is planning near-term missions to Mars that will include chemical processes for converting the carbon dioxide (CO2) and possibly water from the Martian environment to propellants, oxygen, and other useful chemicals. The use of indigenous resources reduces the size and weight of the payloads from Earth significantly, representing enormous cost savings that make human exploration of Mars affordable. Extraterrestrial chemical processing plants will need to be compact, lightweight, highly efficient under reduced gravity, and extraordinarily reliable for long periods. Microchemical and thermal systems represent capability for dramatic reduction in size and weight, while offering high reliability through massive parallelization. In situ propellant production (ISPP), one aspect of the ISRU program, involves collecting and pressurizing atmospheric CO2, conversion reactions, chemical separations, heat exchangers, and cryogenic storage. A preliminary system design of an ISPP plant based on microtechnology has demonstrated significant size, weight, and energy efficiency gains over the current NASA baseline. Energy management is a strong driver for Mars-based processes, not only because energy is a scarce resource, but because heat rejection is problematic; the low pressure environment makes convective heat transfer ineffective. Energy efficiency gains are largely achieved in the microchemical plant through extensive heat recuperation and energy cascading, which has a small size and weight penalty because the added micro heat exchangers are small. This leads to additional size and weight gains by reducing the required area of waste heat radiators. The microtechnology-based ISPP plant is described in detail, including aspects of pinch analysis for optimizing the heat exchanger network. Three options for thermochemical compression Of CO2 from the Martian atmosphere, adsorption, absorption, and cryogenic freezing, are presented, as well as three options for water decomposition, low temperature electrolysis, high temperature electrolysis, and thermochemical decomposition. Other elements of the plant include Sabatier and reverse water gas shift reactors, water recovery, chemical separations, and cryogenic storage. Data are presented supporting preliminary sizing of components, and results of the system design are compared to the existing NASA baseline that is based on conventional technologies.

CHEETAH: A next generation thermochemical code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fried, L.; Souers, P.

1994-11-01

CHEETAH is an effort to bring the TIGER thermochemical code into the 1990s. A wide variety of improvements have been made in Version 1.0. We have improved the robustness and ease of use of TIGER. All of TIGER`s solvers have been replaced by new algorithms. We find that CHEETAH solves a wider variety of problems with no user intervention (e.g. no guesses for the C-J state) than TIGER did. CHEETAH has been made simpler to use than TIGER; typical use of the code occurs with the new standard run command. CHEETAH will make the use of thermochemical codes more attractivemore » to practical explosive formulators. We have also made an extensive effort to improve over the results of TIGER. CHEETAH`s version of the BKW equation of state (BKWC) is able to accurately reproduce energies from cylinder tests; something that other BKW parameter sets have been unable to do. Calculations performed with BKWC execute very quickly; typical run times are under 10 seconds on a workstation. In the future we plan to improve the underlying science in CHEETAH. More accurate equations of state will be used in the gas and the condensed phase. A kinetics capability will be added to the code that will predict reaction zone thickness. Further ease of use features will eventually be added; an automatic formulator that adjusts concentrations to match desired properties is planned.« less

Multi-step approach for comparing the local air pollution contributions of conventional and innovative MSW thermo-chemical treatments.

PubMed

Ragazzi, M; Rada, E C

2012-10-01

In the sector of municipal solid waste management the debate on the performances of conventional and novel thermo-chemical technologies is still relevant. When a plant must be constructed, decision makers often select a technology prior to analyzing the local environmental impact of the available options, as this type of study is generally developed when the design of the plant has been carried out. Additionally, in the literature there is a lack of comparative analyses of the contributions to local air pollution from different technologies. The present study offers a multi-step approach, based on pollutant emission factors and atmospheric dilution coefficients, for a local comparative analysis. With this approach it is possible to check if some assumptions related to the advantages of the novel thermochemical technologies, in terms of local direct impact on air quality, can be applied to municipal solid waste treatment. The selected processes concern combustion, gasification and pyrolysis, alone or in combination. The pollutants considered are both carcinogenic and non-carcinogenic. A case study is presented concerning the location of a plant in an alpine region and its contribution to the local air pollution. Results show that differences among technologies are less than expected. Performances of each technology are discussed in details. Copyright © 2012 Elsevier Ltd. All rights reserved.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions

NASA Astrophysics Data System (ADS)

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F.; van Bokhoven, Jeroen A.

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

Perspectives of advanced thermal management in solar thermochemical syngas production using a counter-flow solid-solid heat exchanger

NASA Astrophysics Data System (ADS)

Falter, Christoph; Sizmann, Andreas; Pitz-Paal, Robert

2017-06-01

A modular reactor model is presented for the description of solar thermochemical syngas production involving counter-flow heat exchangers that recuperate heat from the solid phase. The development of the model is described including heat diffusion within the reactive material as it travels through the heat exchanger, which was previously identified to be a possibly limiting factor in heat exchanger design. Heat transfer within the reactive medium is described by conduction and radiation, where the former is modeled with the three-resistor model and the latter with the Rosseland diffusion approximation. The applicability of the model is shown by the analysis of heat exchanger efficiency for different material thicknesses and porosities in a system with 8 chambers and oxidation and reduction temperatures of 1000 K and 1800 K, respectively. Heat exchanger efficiency is found to rise strongly for a reduction of material thickness, as the element mass is reduced and a larger part of the elements takes part in the heat exchange process. An increase of porosity enhances radiation heat exchange but deteriorates conduction. The overall heat exchange in the material is improved for high temperatures in the heat exchanger, as radiation dominates the energy transfer. The model is shown to be a valuable tool for the development and analysis of solar thermochemical reactor concepts involving heat exchange from the solid phase.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions.

PubMed

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F; van Bokhoven, Jeroen A

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

A rapid burst in hotspot motion through the interaction of tectonics and deep mantle flow.

PubMed

Hassan, Rakib; Müller, R Dietmar; Gurnis, Michael; Williams, Simon E; Flament, Nicolas

2016-05-12

Volcanic hotspot tracks featuring linear progressions in the age of volcanism are typical surface expressions of plate tectonic movement on top of narrow plumes of hot material within Earth's mantle. Seismic imaging reveals that these plumes can be of deep origin--probably rooted on thermochemical structures in the lower mantle. Although palaeomagnetic and radiometric age data suggest that mantle flow can advect plume conduits laterally, the flow dynamics underlying the formation of the sharp bend occurring only in the Hawaiian-Emperor hotspot track in the Pacific Ocean remains enigmatic. Here we present palaeogeographically constrained numerical models of thermochemical convection and demonstrate that flow in the deep lower mantle under the north Pacific was anomalously vigorous between 100 million years ago and 50 million years ago as a consequence of long-lasting subduction systems, unlike those in the south Pacific. These models show a sharp bend in the Hawaiian-Emperor hotspot track arising from the interplay of plume tilt and the lateral advection of plume sources. The different trajectories of the Hawaiian and Louisville hotspot tracks arise from asymmetric deformation of thermochemical structures under the Pacific between 100 million years ago and 50 million years ago. This asymmetric deformation waned just before the Hawaiian-Emperor bend developed, owing to flow in the deepest lower mantle associated with slab descent in the north and south Pacific.

Beneficial effects of substituting trivalent ions in the B-site of La0.5Sr0.5Mn1-xAxO3 (A = Al, Ga, Sc) on the thermochemical generation of CO and H2 from CO2 and H2O.

PubMed

Dey, Sunita; Naidu, B S; Rao, C N R

2016-02-14

The effect of substitution of Al(3+), Ga(3+) and Sc(3+) ions in the Mn(3+) site of La0.5Sr0.5MnO3 on the thermochemical splitting of CO2 to generate CO has been studied in detail. Both La0.5Sr0.5Mn1-xGaxO3 and La0.5Sr0.5Mn1-xScxO3 give high yields of O2 and generate CO more efficiently than La0.5Sr0.5Mn1-xAlxO3 or the parent La0.5Sr0.5MnO3. Substitution of even 5% Sc(3+) (x = 0.05) results in a remarkable improvement in performance. Thus La0.5Sr0.5Mn0.95Sc0.05O3 produces 417 μmol g(-1) of O2 and 545 μmol g(-1) of CO, respectively, i.e. 2 and 1.7 times more O2 and CO than La0.5Sr0.5MnO3. This manganite also generates H2 satisfactorily by the thermochemical splitting of H2O.

Kinetics of thermochemical gas-solid reactions important in the Venus sulfur cycle

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.

1988-01-01

The thermochemical net reaction CaCO3 + SO2 yields CaSO4 + CO is predicted to be an important sink for incorporation of SO2 into the Venus crust. The reaction rate law was established to understand the dependence of rate on experimental variables such as temperature and partial pressure of SO2, CO2, and O2. The experimental approach was a variant of the thermogravimetric method often employed to study the kinetics of thermochemical gas-solid reactions. Clear calcite crystals were heated at constant temperature in SO2-bearing gas streams for varying time periods. Reaction rate was determined by three independent methods. A weighted linear least squares fit to all rate data yielded a rate equation. Based on the Venera 13, 14 and Vega 2 observations of CaO content of the Venus atmosphere, SO2 at the calculated rate would be removed from the Venus atmosphere in about 1,900,00 years. The most plausible endogenic source of the sulfur needed to replenish atmospheric SO2 is volcanism. The annual amount of erupted material needed for the replenishment depends on sulfur content; three ratios are used to calculate rates ranging from 0.4 to 11 cu km/year. This geochemically derived volcanism rate can be used to test if geophysically derived rates are correct. The work also suggests that Venus is less volcanically active than the Earth.

Inertial effects on thermochemically driven convection and hydromagnetic dynamos in a spherical shell

NASA Astrophysics Data System (ADS)

Šimkanin, Ján; Kyselica, Juraj; Guba, Peter

2018-03-01

We investigate the thermochemical convection and hydromagnetic dynamos in a spherical shell using the so-called codensity formulation with different buoyancy sources: the secular cooling from the mantle, the buoyancy sources due to the solidification at the inner core boundary and the combination of the two sources. Numerical simulations of the fully non-linear problem are performed using the PARODY code. In the thermochemical regime, we find that when the Prandtl numbers are lower than Ekman numbers, inertial convection is preferred, while the large-scale columnar convection is preferred otherwise. Unlike the large-scale convection, the inertial convection is found to be almost independent of the nature of driving buoyancy source. Moreover, the codensity field evolves to a new, radially symmetric stationary state. At the Ekman numbers much smaller than the Prandtl numbers, we have obtained the westward equatorial zonal flow in the chemically driven regime, while for the other cases zonal flows are eastward near the equator. In the dynamo regime, inertial convection is preferred when the Prandtl numbers are lower than Ekman numbers and the generated dipolar magnetic fields oscillate from the polar region to the mid-latitudes and back. In this case, the generated magnetic fields are independent of the type of buoyancy source. At the Prandtl numbers greater than Ekman numbers, both dipolar and hemispherical dynamos are found.

Nonmetallic materials handbook. Volume 1: Epoxy materials

NASA Technical Reports Server (NTRS)

Podlaseck, S. E.

1979-01-01

Thermochemical and other properties data is presented for the following types of epoxy materials: adhesives, coatings finishes, inks, electrical insulation, encapsulants, sealants, composite laminates, tapes, and thermal insulators.

An experimental test plan for the characterization of molten salt thermochemical properties in heat transport systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pattrick Calderoni

2010-09-01

Molten salts are considered within the Very High Temperature Reactor program as heat transfer media because of their intrinsically favorable thermo-physical properties at temperatures starting from 300 C and extending up to 1200 C. In this context two main applications of molten salt are considered, both involving fluoride-based materials: as primary coolants for a heterogeneous fuel reactor core and as secondary heat transport medium to a helium power cycle for electricity generation or other processing plants, such as hydrogen production. The reference design concept here considered is the Advanced High Temperature Reactor (AHTR), which is a large passively safe reactormore » that uses solid graphite-matrix coated-particle fuel (similar to that used in gas-cooled reactors) and a molten salt primary and secondary coolant with peak temperatures between 700 and 1000 C, depending upon the application. However, the considerations included in this report apply to any high temperature system employing fluoride salts as heat transfer fluid, including intermediate heat exchangers for gas-cooled reactor concepts and homogenous molten salt concepts, and extending also to fast reactors, accelerator-driven systems and fusion energy systems. The purpose of this report is to identify the technical issues related to the thermo-physical and thermo-chemical properties of the molten salts that would require experimental characterization in order to proceed with a credible design of heat transfer systems and their subsequent safety evaluation and licensing. In particular, the report outlines an experimental R&D test plan that would have to be incorporated as part of the design and operation of an engineering scaled facility aimed at validating molten salt heat transfer components, such as Intermediate Heat Exchangers. This report builds on a previous review of thermo-physical properties and thermo-chemical characteristics of candidate molten salt coolants that was generated as part of the same project [1]. However, this work focuses on two materials: the LiF-BeF2 eutectic (67 and 33 mol%, respectively, also known as flibe) as primary coolant and the LiF-NaF-KF eutectic (46.5, 11.5, and 52 mol%, respectively, also known as flinak) as secondary heat transport fluid. At first common issues are identified, involving the preparation and purification of the materials as well as the development of suitable diagnostics. Than issues specific to each material and its application are considered, with focus on the compatibility with structural materials and the extension of the existing properties database.« less

Studies of thermochemical water-splitting cycles

NASA Technical Reports Server (NTRS)

Remick, R. J.; Foh, S. E.

1980-01-01

Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

Hydrogen production from solar energy

NASA Technical Reports Server (NTRS)

Eisenstadt, M. M.; Cox, K. E.

1975-01-01

Three alternatives for hydrogen production from solar energy have been analyzed on both efficiency and economic grounds. The analysis shows that the alternative using solar energy followed by thermochemical decomposition of water to produce hydrogen is the optimum one. The other schemes considered were the direct conversion of solar energy to electricity by silicon cells and water electrolysis, and the use of solar energy to power a vapor cycle followed by electrical generation and electrolysis. The capital cost of hydrogen via the thermochemical alternative was estimated at $575/kW of hydrogen output or $3.15/million Btu. Although this cost appears high when compared with hydrogen from other primary energy sources or from fossil fuel, environmental and social costs which favor solar energy may prove this scheme feasible in the future.

Novel Fabrication of Biodegradable Superabsorbent Microspheres with Diffusion Barrier through Thermo-Chemical Modification and Their Potential Agriculture Applications for Water Holding and Sustained Release of Fertilizer.

PubMed

Feng, Diejing; Bai, Bo; Wang, Honglun; Suo, Yourui

2017-07-26

Synergistic utilization of water and fertilizer has vital contribution to the modern production of agriculture. This work reports on a simple and facile strategy to prepare biodegradable yeast/sodium alginate/poly(vinyl alcohol) superabsorbent microspheres with a diffusion barrier merit by thermo-chemical modification route. The integrated performances, including water absorbency, water retention, water evaporation ratio, leaching loss control, sustained-release behaviors, and degradation in soil, were systematically investigated. The results revealed that the modified microspheres were a triumphant water and fertilizer manager to effectively hold water and control the unexpected leakage of fertilizer for sustained release. Therefore, this work provides a promising approach to ameliorate the utilization efficiency of water and fertilizer in potential agriculture applications.

Supercritical Fluids Processing of Biomass to Chemicals and Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Olson, Norman K.

2011-09-28

The main objective of this project is to develop and/or enhance cost-effective methodologies for converting biomass into a wide variety of chemicals, fuels, and products using supercritical fluids. Supercritical fluids will be used both to perform reactions of biomass to chemicals and products as well as to perform extractions/separations of bio-based chemicals from non-homogeneous mixtures. This work supports the Biomass Program’s Thermochemical Platform Goals. Supercritical fluids are a thermochemical approach to processing biomass that, while aligned with the Biomass Program’s interests in gasification and pyrolysis, offer the potential for more precise and controllable reactions. Indeed, the literature with respect tomore » the use of water as a supercritical fluid frequently refers to “supercritical water gasification” or “supercritical water pyrolysis.”« less

G3X-K theory: A composite theoretical method for thermochemical kinetics

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2013-02-01

A composite theoretical method for accurate thermochemical kinetics, G3X-K, is described. This method is accurate to around 0.5 kcal mol-1 for barrier heights and 0.8 kcal mol-1 for enthalpies of formation. G3X-K is a modification of G3SX theory using the M06-2X density functional for structures and zero-point energies and parameterized for a test set of 223 heats of formation and 23 barrier heights. A reduced perturbation-order variant, G3X(MP3)-K, is also developed, providing around 0.7 kcal mol-1 accuracy for barrier heights and 0.9 kcal mol-1 accuracy for enthalpies, at reduced computational cost. Some opportunities to further improve Gn composite methods are identified and briefly discussed.

Moving bed reactor for solar thermochemical fuel production

DOEpatents

Ermanoski, Ivan

2013-04-16

Reactors and methods for solar thermochemical reactions are disclosed. Embodiments of reactors include at least two distinct reactor chambers between which there is at least a pressure differential. In embodiments, reactive particles are exchanged between chambers during a reaction cycle to thermally reduce the particles at first conditions and oxidize the particles at second conditions to produce chemical work from heat. In embodiments, chambers of a reactor are coupled to a heat exchanger to pre-heat the reactive particles prior to direct exposure to thermal energy with heat transferred from reduced reactive particles as the particles are oppositely conveyed between the thermal reduction chamber and the fuel production chamber. In an embodiment, particle conveyance is in part provided by an elevator which may further function as a heat exchanger.

Significance of vapor phase chemical reactions on CVD rates predicted by chemically frozen and local thermochemical equilibrium boundary layer theories

NASA Technical Reports Server (NTRS)

Gokoglu, Suleyman A.

1988-01-01

This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.

Computational aerothermodynamics

NASA Technical Reports Server (NTRS)

Deiwert, George S.

1989-01-01

Computational aerothermodynamics concerns the coupling of real gas effects with equations of motion to include thermochemical rate processes for chemical and energy exchange phenomena. These processes concern the creation and destruction of gas species by chemical reactions and the transfer of energy between the various species and between the various energy modes (e.g., translation, rotation, vibration, ionization, dissociation/recombination, etc.) of the species. To gain some insight into when such phenomena occur for current and future aerospace flight vehicles the author shows the flight regimes of some typical vehicles (e.g., Concord, aerospace plane, Space Shuttle, associated space transfer vehicles, Apollo entry vehicle, etc.) in terms of flight altitude and flight speed. Also indicated are regimes where chemical reactions such as dissociation and ionization are important and where nonequilibrium thermochemical phenomena are important.

Doped calcium manganites for advanced high-temperature thermochemical energy storage

DOE PAGES

Babiniec, Sean M.; Coker, Eric N.; Miller, James E.; ...

2015-12-16

Developing efficient thermal storage for concentrating solar power plants is essential to reducing the cost of generated electricity, extending or shifting the hours of operation, and facilitating renewable penetration into the grid. Perovskite materials of the CaB xMn 1-xO 3-δ family, where B = Al or Ti, promise improvements in cost and energy storage density over other perovskites currently under investigation. Thermogravimetric analysis of the thermal reduction and reoxidation of these materials was used to extract equilibrium thermodynamic parameters. Lastly, the results demonstrate that these novel thermochemical energy storage media display the highest reaction enthalpy capacity for perovskites reported tomore » date, with a reaction enthalpy of 390 kJ/kg, a 56% increase over previously reported compositions.« less

High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daniel A. Mosher; Xia Tang; Ronald J. Brown

2007-07-27

This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchangermore » optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.« less

Chemical nonequilibrium effects on the inviscid flow in the windward plane of symmetry of two simplified shuttle configurations

NASA Technical Reports Server (NTRS)

Lordi, J. A.; Vidal, R. J.; Johnson, C. B.

1973-01-01

A theoretical study was made to delineate the effects of thermochemical nonequilibrium in the inviscid flow field of a representative space shuttle orbiter configuration. The study was based on experimental pressure data which was used as an input to a stream tube computer program. The pressure data from two configurations are tabulated. Calculations were restricted to the windward plane of symmetry and the calculations covered an altitude range from 200,000 to 250,000 feet at velocities of 16,000 to 24,000 feet per second respectively. Angles of attack of 20 and 40 degrees were included. The calculations show that the nonequilibrium effects are confined largely to the entropy layer expect at the highest altitude, where significant nonequilibrium effects are observed in the entire inviscid flow field.

Marc Pomeroy | NREL

Science.gov Websites

sampling of on-stream components of thermochemical biomass conversion in real-time Affiliated Research Integration, Scale-Up, and Piloting Areas of Expertise Analytical sampling of hot gas and vapor phase products

On the Fracture Toughness and Crack Growth Resistance of Bio-Inspired Thermal Spray Hybrid Composites

NASA Astrophysics Data System (ADS)

Resnick, Michael Murray

Surface exploration of the Moon and Asteroids can provide important information to scientists regarding the origins of the solar-system and life . Small robots and sensor modules can enable low-cost surface exploration. In the near future, they are the main machines providing these answers. Advanced in electronics, sensors and actuators enable ever smaller platforms, with compromising functionality. However similar advances haven't taken place for power supplies and thermal control system. The lunar south pole has temperatures in the range of -100 to -150 °C. Similarly, asteroid surfaces can encounter temperatures of -150 °C. Most electronics and batteries do not work below -40 °C. An effective thermal control system is critical towards making small robots and sensors module for extreme environments feasible. In this work, the feasibility of using thermochemical storage materials as a possible thermal control solution is analyzed for small robots and sensor modules for lunar and asteroid surface environments. The presented technology will focus on using resources that is readily generated as waste product aboard a spacecraft or is available off-world through In-Situ Resource Utilization (ISRU). In this work, a sensor module for extreme environment has been designed and prototyped. Our intention is to have a network of tens or hundreds of sensor modules that can communicate and interact with each other while also gathering science data. The design contains environmental sensors like temperature sensors and IMU (containing accelerometer, gyro and magnetometer) to gather data. The sensor module would nominally contain an electrical heater and insulation. The thermal heating effect provided by this active heater is compared with the proposed technology that utilizes thermochemical storage chemicals. Our results show that a thermochemical storage-based thermal control system is feasible for use in extreme temperatures. A performance increase of 80% is predicted for the sensor modules on the asteroid Eros using thermochemical based storage system. At laboratory level, a performance increase of 8 to 9 % is observed at ambient temperatures of -32°C and -40 °C.

Solar fuels production as a sustainable alternative for substituting fossil fuels: COSOLπ project

NASA Astrophysics Data System (ADS)

Hernando Romero-Paredes, R.; Alvarado-Gil, Juan José; Arancibia-Bulnes, Camilo Alberto; Ramos-Sánchez, Víctor Hugo; Villafán-Vidales, Heidi Isabel; Espinosa-Paredes, Gilberto; Abanades, Stéphane

2017-06-01

This article presents, in summary form, the characteristics of COSOLπ development project and some of the results obtained to date. The benefits of the work of this project will include the generation of a not polluting transportable energy feedstock from a free, abundant and available primary energy source, in an efficient method with no greenhouse gas emission. This will help to ensure energy surety to a future transportation/energy infrastructure, without any fuel import. Further technological development of thermochemical production of clean fuels, together with solar reactors and also with the possibility of determining the optical and thermal properties of the materials involved a milestone in the search for new processes for industrialization. With the above in mind, important national academic institutions: UAM, UNAM, CINVESTAV, UACH, UNISON among others, have been promoting research in solar energy technologies. The Goals and objectives are to conduct research and technological development driving high-temperature thermochemical processes using concentrated solar radiation as thermal energy source for the future sustainable development of industrial processes. It focuses on the production of clean fuels such as H2, syngas, biofuels, without excluding the re-value of materials used in the industry. This project conducts theoretical and experimental studies for the identification, characterization, and optimization of the most promising thermochemical cycles, and for the thorough investigation of the reactive chemical systems. It applies material science and nano-engineering to improve chemicals properties and stability upon cycling. The characterization of materials will serve to measure the chemical composition and purity (MOX fraction-1) of each of the samples. The characterizations also focus on the solid particle morphology (shape, size, state of aggregation, homogeneity, specific surface) images obtained from SEM / TEM and BET measurements. Likewise will the thermal and optical characterization of the influence that these parameters represent in the solar reactor. The experimental and theoretical results obtained for each redox system will be compared and analyzed to determine the cycle with the highest potential. Advances on simulation, design, construction and experimentation on solar reactors to conduct thermochemical splitting water reactions are presented.

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments

PubMed Central

Olsson-Francis, Karen; Pearson, Victoria K.; Steer, Elisabeth D.; Schwenzer, Susanne P.

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 107, zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in “simpler” secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars. PMID:28943863

Determination of Geochemical Bio-Signatures in Mars-Like Basaltic Environments.

PubMed

Olsson-Francis, Karen; Pearson, Victoria K; Steer, Elisabeth D; Schwenzer, Susanne P

2017-01-01

Bio-signatures play a central role in determining whether life existed on early Mars. Using a terrestrial basalt as a compositional analog for the martian surface, we applied a combination of experimental microbiology and thermochemical modeling techniques to identify potential geochemical bio-signatures for life on early Mars. Laboratory experiments were used to determine the short-term effects of biota on the dissolution of terrestrial basalt, and the formation of secondary alteration minerals. The chemoorganoheterotrophic bacterium, Burkholderia sp. strain B_33, was grown in a minimal growth medium with and without terrestrial basalt as the sole nutrient source. No growth was detected in the absence of the basalt. In the presence of basalt, during exponential growth, the pH decreased rapidly from pH 7.0 to 3.6 and then gradually increased to a steady-state of equilibrium of between 6.8 and 7.1. Microbial growth coincided with an increase in key elements in the growth medium (Si, K, Ca, Mg, and Fe). Experimental results were compared with theoretical thermochemical modeling to predict growth of secondary alteration minerals, which can be used as bio-signatures, over a geological timescale. We thermochemically modeled the dissolution of the basalt (in the absence of biota) in very dilute brine at 25°C, 1 bar; the pH was buffered by the mineral dissolution and precipitation reactions. Preliminary results suggested that at the water to rock ratio of 1 × 10 7 , zeolite, hematite, chlorite, kaolinite, and apatite formed abiotically. The biotic weathering processes were modeled by varying the pH conditions within the model to adjust for biologic influence. The results suggested that, for a basaltic system, the microbially-mediated dissolution of basalt would result in "simpler" secondary alteration, consisting of Fe-hydroxide and kaolinite, under conditions where the abiotic system would also form chlorite. The results from this study demonstrate that, by using laboratory-based experiments and thermochemical modeling, it is possible to identify secondary alteration minerals that could potentially be used to distinguish between abiotic and biotic weathering processes on early Mars. This work will contribute to the interpretation of data from past, present, and future life detection missions to Mars.

Process for thermochemically producing hydrogen

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1976-01-01

Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water.

Kinetic calculations of explosives with slow-burning constituents

NASA Astrophysics Data System (ADS)

Howard, W. Michael; Souers, P. Clark; Fried, Laurence E.

1998-07-01

The equilibrium thermochemical code CHEETAH V1.40 has been modified to detonate part of the explosive and binder. An Einstein thermal description of the unreacted constituents is used, and the Einstein temperature may be increased to reduce heat absorption. We study the effect of the reactivity and thermal transport on the detonation velocity. Hydroxy-terminated-polybutadiene binders have low energy and density and would degrade the detonation velocity if they burned. Runs with unburned binder are closer to the measured values. Aluminum and ammonium perchlorate are also largely unburned within the sonic reaction zone that determines the detonation velocity. All three materials appear not to fully absorb heat as well. The normal assumption of total reaction in a thermochemical code is clearly not true for these special cases, where the detonation velocities have widely different values for different combinations of processes.

Research and evaluation of biomass resources/conversion/utilization systems. Biomass allocation model. Volume 1: Test and appendices A & B

NASA Astrophysics Data System (ADS)

Stringer, R. P.; Ahn, Y. K.; Chen, H. T.; Helm, R. W.; Nelson, E. T.; Shields, K. J.

1981-08-01

A biomass allocation model was developed to show the most profitable combination of biomass feedstocks, thermochemical conversion processes, and fuel products to serve the seasonal conditions in a regional market. This optimization model provides a tool for quickly calculating which of a large number of potential biomass missions is the most profitable mission. Other components of the system serve as a convenient storage and retrieval mechanism for biomass marketing and thermochemical conversion processing data. The system can be accessed through the use of a computer terminal, or it could be adapted to a microprocessor. A User's Manual for the system is included. Biomass derived fuels included in the data base are the following: medium Btu gas, low Btu gas, substitute natural gas, ammonia, methanol, electricity, gasoline, and fuel oil.

The influence of Ag content and annealing time on structural and optical properties of SGS antimony-germanate glass doped with Er3+ ions

NASA Astrophysics Data System (ADS)

Zmojda, J.; Kochanowicz, M.; Miluski, P.; Baranowska, A.; Basa, A.; Jadach, R.; Sitarz, M.; Dorosz, D.

2018-05-01

A series of erbium doped SGS antimony-germanate glass embedding silver (Ag0) nanoparticles have been synthesized by a one-step melt-quench thermochemical reduction technique. The effect of NPs concentration and annealing time on the structural and photoluminescent (PL) properties were investigated. The Raman spectra as a function of temperature measured in-situ allow to determine the structural changes in vicinity of Ag+ ions and confirmed thermochemical reduction of Ag+ ions by Sb3+ ions. The surface plasmon resonance absorption band was evidenced near 450 nm. The impact of local field effect generated by Ag0 nanoparticles (NPs) and energy transfer from surface of silver NPs to trivalent erbium ions on near-infrared and up-conversion luminescence was described in terms of enhancement and quench phenomena.

Thermo-chemical pretreatment and enzymatic hydrolysis for enhancing saccharification of catalpa sawdust.

PubMed

Jin, Shuguang; Zhang, Guangming; Zhang, Panyue; Li, Fan; Fan, Shiyang; Li, Juan

2016-04-01

To improve the reducing sugar production from catalpa sawdust, thermo-chemical pretreatments were examined and the chemicals used including NaOH, Ca(OH)2, H2SO4, and HCl. The hemicellulose solubilization and cellulose crystallinity index (CrI) were significantly increased after thermo-alkaline pretreatments, and the thermo-Ca(OH)2 pretreatment showed the best improvement for reducing sugar production comparing to other three pretreatments. The conditions of thermo-Ca(OH)2 pretreatment and enzymatic hydrolysis were systematically optimized. Under the optimal conditions, the reducing sugar yield increased by 1185.7% comparing to the control. This study indicates that the thermo-Ca(OH)2 pretreatment is ideal for the saccharification of catalpa sawdust and that catalpa sawdust is a promising raw material for biofuel. Copyright © 2016 Elsevier Ltd. All rights reserved.

Combining mineral physics with seismic observations: What can we deduce about the thermochemical structure of the Earth's deep interior?

NASA Astrophysics Data System (ADS)

Cobden, L. J.

2017-12-01

Mineral physics provides the essential link between seismic observations of the Earth's interior, and laboratory (or computer-simulated) measurements of rock properties. In this presentation I will outline the procedure for quantitative conversion from thermochemical structure to seismic structure (and vice versa) using the latest datasets from seismology and mineralogy. I will show examples of how this method can allow us to infer major chemical and dynamic properties of the deep mantle. I will also indicate where uncertainties and limitations in the data require us to exercise caution, in order not to "over-interpret" seismic observations. Understanding and modelling these uncertainties serves as a useful guide for mineralogists to ascertain which mineral parameters are most useful in seismic interpretation, and enables seismologists to optimise their data assembly and inversions for quantitative interpretations.

Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

NASA Astrophysics Data System (ADS)

Qian, Hong; Kjelstrup, Signe; Kolomeisky, Anatoly B.; Bedeaux, Dick

2016-04-01

Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

Continuous thermochemical conversion process to produce oil from swine manure

USGS Publications Warehouse

Ocfemia, K.; Zhang, Y.; Funk, T.; Christianson, L.; Chen, S.

2004-01-01

Thermochemical conversion (TCC) of livestock manure is a novel technology that has shown very promising results in treating waste and producing oil. A batch TCC system that was previously developed successfully converted 70% of swine manure volatile solids to oil and reduced manure chemical oxygen demand by ??? 75%. The necessary retention time to achieve an oil product was largely dependent on the operating temperature. The highest oil production efficiency was 80% of the volatile solids (or 70 wt % of the total solids). The average carbon and hydrogen contents were ??? 72 and 9%, respectively. The heating values for 80% of the oil products ranged from 32,000 to 36,700 kJ/kg. This is an abstract of a paper presented at the AWMA 97th Annual Conference and Exhibition (Indianapolis, IN 6/22-25/2004).

Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

PubMed

Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

2015-01-07

Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

Thermochemical characterization of some thermally stable thermoplastic and thermoset polymers

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Gilwee, W. J., Jr.; Parker, J. A.

1979-01-01

The thermochemical and flammability properties of some thermally stable polymers considered for use in aircraft interiors are described. The properties studied include: (1) thermomechanical properties such as glass transition and melt temperature; (2) dynamic thermogravimetric analysis in anaerobic environment; (3) flammability properties such as oxygen index, flame spread, and smoke evolution; and (4) selected physical properties. The thermoplastic polymers evaluated include polyphenylene sulfide, polyaryl sulfone, 9,9-bis(4-hydroxyphenyl)-fluorene polycarbonate-poly(dimethylsiloxane) and polyether sulfone. The thermoset polymers evaluated include epoxy, bismaleimide, a modified phenolic, and polyaromatic melamine resin. These resins were primarily used in the fabrication of glass-reinforced prepregs for the construction of experimental panels. Test results and relative rankings of some of the flammability parameters are presented, and the relationship of the molecular structure, char yield, and flammability properties of these polymers are discussed.

Innovative pretreatment strategies for biogas production.

PubMed

Patinvoh, Regina J; Osadolor, Osagie A; Chandolias, Konstantinos; Sárvári Horváth, Ilona; Taherzadeh, Mohammad J

2017-01-01

Biogas or biomethane is traditionally produced via anaerobic digestion, or recently by thermochemical or a combination of thermochemical and biological processes via syngas (CO and H 2 ) fermentation. However, many of the feedstocks have recalcitrant structure and are difficult to digest (e.g., lignocelluloses or keratins), or they have toxic compounds (such as fruit flavors or high ammonia content), or not digestible at all (e.g., plastics). To overcome these challenges, innovative strategies for enhanced and economically favorable biogas production were proposed in this review. The strategies considered are commonly known physical pretreatment, rapid decompression, autohydrolysis, acid- or alkali pretreatments, solvents (e.g. for lignin or cellulose) pretreatments or leaching, supercritical, oxidative or biological pretreatments, as well as combined gasification and fermentation, integrated biogas production and pretreatment, innovative biogas digester design, co-digestion, and bio-augmentation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Additive erosion reduction influences in the turbulent boundary layer

NASA Astrophysics Data System (ADS)

Buckingham, A. C.

1981-05-01

Results of a sequence of flow, heat and mass transfer calculations are presented which theoretically characterize the erosive environment at the wall surface of refractory metal coated and uncoated gun barrels. The theoretical results include analysis of the wall surface temperature, heat flux, and shear stress time histories on thin (10 mil.) Cr, Mo, Nb, and Ta plated steel barrel walls as uncoated steel walls. The calculations combine effects of a number of separate processes which were previously (and purposely) studied individually. These include solid particle additive concentrations, gas wall thermochemical influences, and transient turbulent wall boundary layer flow with multicomponent molecular diffusion and reactions from interaction of propellant combustion and the eroding surface. The boundary layer model includes particulate additive concentrations as well as propellant combustion products, considered for the present to be in the local thermochemical equilibrium.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

PubMed Central

2013-01-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction. PMID:23601907

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

NASA Astrophysics Data System (ADS)

Wen, John Z.; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F.; Zhou, Y. Norman

2013-04-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites.

PubMed

Wen, John Z; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F; Zhou, Y Norman

2013-04-20

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Some current problems in oxidation kinetics

NASA Technical Reports Server (NTRS)

Benson, S. W.

1972-01-01

Experimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.

Ethanol extraction of phytosterols from corn fiber

DOEpatents

Abbas, Charles; Beery, Kyle E.; Binder, Thomas P.; Rammelsberg, Anne M.

2010-11-16

The present invention provides a process for extracting sterols from a high solids, thermochemically hydrolyzed corn fiber using ethanol as the extractant. The process includes obtaining a corn fiber slurry having a moisture content from about 20 weight percent to about 50 weight percent solids (high solids content), thermochemically processing the corn fiber slurry having high solids content of 20 to 50% to produce a hydrolyzed corn fiber slurry, dewatering the hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, washing the residual corn fiber, dewatering the washed, hydrolyzed corn fiber slurry to achieve a residual corn fiber having a moisture content from about 30 to 80 weight percent solids, and extracting the residual corn fiber with ethanol and separating at least one sterol.

Nuclear driven water decomposition plant for hydrogen production

NASA Technical Reports Server (NTRS)

Parker, G. H.; Brecher, L. E.; Farbman, G. H.

1976-01-01

The conceptual design of a hydrogen production plant using a very-high-temperature nuclear reactor (VHTR) to energize a hybrid electrolytic-thermochemical system for water decomposition has been prepared. A graphite-moderated helium-cooled VHTR is used to produce 1850 F gas for electric power generation and 1600 F process heat for the water-decomposition process which uses sulfur compounds and promises performance superior to normal water electrolysis or other published thermochemical processes. The combined cycle operates at an overall thermal efficiency in excess of 45%, and the overall economics of hydrogen production by this plant have been evaluated predicated on a consistent set of economic ground rules. The conceptual design and evaluation efforts have indicated that development of this type of nuclear-driven water-decomposition plant will permit large-scale economic generation of hydrogen in the 1990s.

Effects of Dopant Metal Variation and Material Synthesis Method on the Material Properties of Mixed Metal Ferrites in Yttria Stabilized Zirconia for Solar Thermochemical Fuel Production

DOE PAGES

Leonard, Jeffrey; Reyes, Nichole; Allen, Kyle M.; ...

2015-01-01

Mixed metal ferrites have shown much promise in two-step solar-thermochemical fuel production. Previous work has typically focused on evaluating a particular metal ferrite produced by a particular synthesis process, which makes comparisons between studies performed by independent researchers difficult. A comparative study was undertaken to explore the effects different synthesis methods have on the performance of a particular material during redox cycling using thermogravimetry. This study revealed that materials made via wet chemistry methods and extended periods of high temperature calcination yield better redox performance. Differences in redox performance between materials made via wet chemistry methods were minimal and thesemore » demonstrated much better performance than those synthesized via the solid state method. Subsequently, various metal ferrite samples (NiFe 2 O 4 , MgFe 2 O 4 , CoFe 2 O 4 , and MnFe 2 O 4 ) in yttria stabilized zirconia (8YSZ) were synthesized via coprecipitation and tested to determine the most promising metal ferrite combination. It was determined that 10 wt.% CoFe 2 O 4 in 8YSZ produced the highest and most consistent yields of O 2 and CO. By testing the effects of synthesis methods and dopants in a consistent fashion, those aspects of ferrite preparation which are most significant can be revealed. More importantly, these insights can guide future efforts in developing the next generation of thermochemical fuel production materials.« less

Pretreatment of Cottage Cheese to Enhance Biogas Production

PubMed Central

Salgaonkar, Bhakti; Mutnuri, Srikanth

2014-01-01

This study evaluated the possibility of pretreating selected solid fraction of an anaerobic digester treating food waste to lower the hydraulic retention time and increase the methane production. The study investigated the effect of different pretreatments (thermal, chemical, thermochemical and enzymatic) for enhanced methane production from cottage cheese. The most effective pretreatments were thermal and enzymatic. Highest solubilisation of COD was observed in thermal pretreatment, followed by thermochemical. In single enzyme systems, lipase at low concentration gave significantly higher methane yield than for the experiments without enzyme additions. The highest lipase dosages decreased methane yield from cottage cheese. However, in case of protease enzyme an increase in concentration of the enzyme showed higher methane yield. In the case of mixed enzyme systems, pretreatment at 1 : 2 ratio of lipase : protease showed higher methane production in comparison with 1 : 1 and 2 : 1 ratios. Methane production potentials for different pretreatments were as follows: thermal 357 mL/g VS, chemical 293 mL/g VS, and thermochemical 441 mL/g VS. The average methane yield from single enzyme systems was 335 mL/g VS for lipase and 328 mL/g VS for protease. Methane potentials for mixed enzyme ratios were 330, 360, and 339 mL/g VS for 1 : 1, 1 : 2, and 2 : 1 lipase : protease, respectively. PMID:24995288

Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mumm, Daniel

2013-08-31

The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leadingmore » to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive/thermo-chemical attack mechanisms; (iv) developing a mechanics-based analysis of the driving forces for crack growth and delamination, based on molten phase infiltration, misfit upon cooling, and loss of compliance; (v) understanding changes in TGO growth mechanisms associated with these emerging combustion product streams; and (vi) identifying degradation resistant alternative materials (including new compositions or bi-layer concepts) for use in mitigating the observed degradation modes. To address the materials stability concerns, this program integrated research thrusts aimed at: (1) Conducting tests in simulated syngas and HHC environments to evaluate materials evolution and degradation mechanisms; assessing thermally grown oxide development unique to HHC environmental exposures; carrying out high-resolution imaging and microanalysis to elucidate the evolution of surface deposits (molten phase formation and infiltration); exploring thermo-chemical instabilities; assessing thermo-mechanical drivers and thermal gradient effects on degradation; and quantitatively measuring stress evolution due to enhanced sintering and thermo-chemical instabilities induced in the coating. (2) Executing experiments to study the melting and infiltration of simulated ash deposits, and identifying reaction products and evolving phases associated with molten phase corrosion mechanisms; utilizing thermal spray techniques to fabricate test coupons with controlled microstructures to study mechanisms of instability and degradation; facilitating thermal gradient testing; and developing new materials systems for laboratory testing; (3) Correlating information on the resulting combustion environments to properly assess materials exposure conditions and guide the development of lab-scale simulations of material exposures; specification of representative syngas and high-hydrogen fuels with realistic levels of impurities and contaminants, to explore differences in heat transfer, surface degradation, and deposit formation; and facilitating combustion rig testing of materials test coupons.« less

Analytical modeling of intumescent coating thermal protection system in a JP-5 fuel fire environment

NASA Technical Reports Server (NTRS)

Clark, K. J.; Shimizu, A. B.; Suchsland, K. E.; Moyer, C. B.

1974-01-01

The thermochemical response of Coating 313 when exposed to a fuel fire environment was studied to provide a tool for predicting the reaction time. The existing Aerotherm Charring Material Thermal Response and Ablation (CMA) computer program was modified to treat swelling materials. The modified code is now designated Aerotherm Transient Response of Intumescing Materials (TRIM) code. In addition, thermophysical property data for Coating 313 were analyzed and reduced for use in the TRIM code. An input data sensitivity study was performed, and performance tests of Coating 313/steel substrate models were carried out. The end product is a reliable computational model, the TRIM code, which was thoroughly validated for Coating 313. The tasks reported include: generation of input data, development of swell model and implementation in TRIM code, sensitivity study, acquisition of experimental data, comparisons of predictions with data, and predictions with intermediate insulation.

A Study of Upgraded Phenolic Curing for RSRM Nozzle Rings

NASA Technical Reports Server (NTRS)

Smartt, Ziba

2000-01-01

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.

Space exploration and the history of solar-system volatiles

NASA Technical Reports Server (NTRS)

Fanale, F. P.

1976-01-01

The thermochemical history of volatile substances in all solar-system planets, satellites, and planetoids is discussed extensively. The volatiles are viewed as an interface between the abiotic and biotic worlds and as a key to the history of bodies of the solar system. A flowsheet of processes and states is exhibited. Differences in bulk volatiles distribution between the planetary bodies and between the interior, surface, and atmosphere of each body are considered, as well as sinks for volatiles in degassing. The volatiles-rich Jovian and Saturnian satellites, the effect of large-planet magnetosphere sweeps on nearby satellites, volatiles of asteroids and comets, and the crucial importance of seismic, gravity, and libration data are treated. A research program encompassing analysis of the elemental and isotopic composition of rare gas in atmospheres, assay of volatiles-containing phases in regoliths, and examination of present or past atmospheric escape/accretion processes is recommended.

Thermochemical nanolithography components, systems, and methods

DOEpatents

Riedo, Elisa; Marder, Seth R.; de Heer, Walt A.; Szoskiewicz, Robert J.; Kodali, Vamsi K.; Jones, Simon C.; Okada, Takashi; Wang, Debin; Curtis, Jennifer E.; Henderson, Clifford L.; Hua, Yueming

2013-06-18

Improved nanolithography components, systems, and methods are described herein. The systems and methods generally employ a resistively heated atomic force microscope tip to thermally induce a chemical change in a surface. In addition, certain polymeric compositions are also disclosed.

Kristin Smith | NREL

Science.gov Websites

Smith Photo of Kristin Smith Kristin Smith Thermochemical Process Design Engineer Kristin.Smith @nrel.gov | 303-384-7877 Orcid ID http://orcid.org/0000-0001-6397-031X Research Interests Kristin Smith is a

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide.

PubMed

Changala, P Bryan; Nguyen, T Lam; Baraban, Joshua H; Ellison, G Barney; Stanton, John F; Bross, David H; Ruscic, Branko

2017-11-22

The adiabatic ionization energy of hydrogen peroxide (HOOH) is investigated, both by means of theoretical calculations and theoretically assisted reanalysis of previous experimental data. Values obtained by three different approaches: 10.638 ± 0.012 eV (purely theoretical determination), 10.649 ± 0.005 eV (reanalysis of photoelectron spectrum), and 10.645 ± 0.010 eV (reanalysis of photoionization spectrum) are in excellent mutual agreement. Further refinement of the latter two values to account for asymmetry of the rotational profile of the photoionization origin band leads to a reduction of 0.007 ± 0.006 eV, which tends to bring them into even closer alignment with the purely theoretical value. Detailed analysis of this fundamental quantity by the Active Thermochemical Tables approach, using the present results and extant literature, gives a final estimate of 10.641 ± 0.006 eV.

Active Thermochemical Tables: The Adiabatic Ionization Energy of Hydrogen Peroxide

DOE PAGES

Changala, P. Bryan; Nguyen, T. Lam; Baraban, Joshua H.; ...

2017-09-07

The adiabatic ionization energy of hydrogen peroxide (HOOH) is investigated, both by means of theoretical calculations and theoretically-assisted reanalysis of previous experimental data. Values obtained by three different approaches: 10.638 ± 0.012 eV (purely theoretical determination), 10.649 ± 0.005 eV (reanalysis of photoelectron spectrum) and 10.645 ± 0.010 eV (reanalysis of photoionization spectrum) are in excellent mutual agreement. Further refinement of the latter two values to account for asymmetry of the rotational profile of the photoionization origin band leads to a reduction of 0.007 ± 0.006 eV, which tends to bring them into even closer alignment with the purely theoreticalmore » value. As a result, detailed analysis of this fundamental quantity by the Active Thermochemical Tables (ATcT) approach, using the present results and extant literature, gives a final estimate of 10.641 ± 0.006 eV.« less

Thermochemical factors affecting the dehalogenation of aromatics.

PubMed

Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

2013-12-17

Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

Comparative study of thermochemical processes for hydrogen production from biomass fuels.

PubMed

Biagini, Enrico; Masoni, Lorenzo; Tognotti, Leonardo

2010-08-01

Different thermochemical configurations (gasification, combustion, electrolysis and syngas separation) are studied for producing hydrogen from biomass fuels. The aim is to provide data for the production unit and the following optimization of the "hydrogen chain" (from energy source selection to hydrogen utilization) in the frame of the Italian project "Filiera Idrogeno". The project focuses on a regional scale (Tuscany, Italy), renewable energies and automotive hydrogen. Decentred and small production plants are required to solve the logistic problems of biomass supply and meet the limited hydrogen infrastructures. Different options (gasification with air, oxygen or steam/oxygen mixtures, combustion, electrolysis) and conditions (varying the ratios of biomass and gas input) are studied by developing process models with uniform hypothesis to compare the results. Results obtained in this work concern the operating parameters, process efficiencies, material and energetic needs and are fundamental to optimize the entire hydrogen chain. Copyright 2010 Elsevier Ltd. All rights reserved.

VUV Dissociative Photoionization of Quinoline in the 7-26 eV Photon Energy Range

NASA Astrophysics Data System (ADS)

Leach, Sydney; Jochims, Hans-Werner; Baumgärtel, Helmut; Champion, Norbert

2018-05-01

The dissociative photoionization of quinoline was studied by photoionization mass spectrometry and ion yield measurements over a synchrotron photon excitation energy range 7-26 eV. The ionic and neutral products were identified with the aid of thermochemical calculations that, in some cases, led to deeper understanding of photodissociation pathways and the determination of upper limits of heats of formation of ionic and neutral dissociation products. A detailed comparison between the 20 eV photon excitation and 70 eV electron impact mass spectra, coupled with estimation of thermochemical appearance energies, leads to assignment of the dissociative ionization cation and neutral products for each detected ion. Reaction schemes for formation of these products are proposed in a number of cases. Ion intensities in the photon and electron impact mass spectra were used to consider extending a rule of charge retention in simple bond cleavage to more complex cases of dissociative ionization.

Review of the Two-Step H2O/CO2-Splitting Solar Thermochemical Cycle Based on Zn/ZnO Redox Reactions

PubMed Central

Loutzenhiser, Peter G.; Meier, Anton; Steinfeld, Aldo

2010-01-01

This article provides a comprehensive overview of the work to date on the two‑step solar H2O and/or CO2 splitting thermochemical cycles with Zn/ZnO redox reactions to produce H2 and/or CO, i.e., synthesis gas—the precursor to renewable liquid hydrocarbon fuels. The two-step cycle encompasses: (1) The endothermic dissociation of ZnO to Zn and O2 using concentrated solar energy as the source for high-temperature process heat; and (2) the non-solar exothermic oxidation of Zn with H2O/CO2 to generate H2/CO, respectively; the resulting ZnO is then recycled to the first step. An outline of the underlying science and the technological advances in solar reactor engineering is provided along with life cycle and economic analyses. PMID:28883361

High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

PubMed

Chueh, William C; Falter, Christoph; Abbott, Mandy; Scipio, Danien; Furler, Philipp; Haile, Sossina M; Steinfeld, Aldo

2010-12-24

Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.

Regeneration of glass nanofluidic chips through a multiple-step sequential thermochemical decomposition process at high temperatures.

PubMed

Xu, Yan; Wu, Qian; Shimatani, Yuji; Yamaguchi, Koji

2015-10-07

Due to the lack of regeneration methods, the reusability of nanofluidic chips is a significant technical challenge impeding the efficient and economic promotion of both fundamental research and practical applications on nanofluidics. Herein, a simple method for the total regeneration of glass nanofluidic chips was described. The method consists of sequential thermal treatment with six well-designed steps, which correspond to four sequential thermal and thermochemical decomposition processes, namely, dehydration, high-temperature redox chemical reaction, high-temperature gasification, and cooling. The method enabled the total regeneration of typical 'dead' glass nanofluidic chips by eliminating physically clogged nanoparticles in the nanochannels, removing chemically reacted organic matter on the glass surface and regenerating permanent functional surfaces of dissimilar materials localized in the nanochannels. The method provides a technical solution to significantly improve the reusability of glass nanofluidic chips and will be useful for the promotion and acceleration of research and applications on nanofluidics.

Assessment of relative flammability and thermochemical properties of some thermoplastic materials

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.

1978-01-01

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermal mechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in an anaerobic and oxidative environment, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers which were evaluated included: acrylonitrile-butadiene-styrene, bisphenol A polycarbonate, bisphenol fluorenone carbonatedimethylsiloxane block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters including molding characteristics of some of the advanced polymers are described. Test results and relative rankings of some of the flammability, smoke and toxicity properties are presented.

Baking sunflower hulls within an aluminum envelope in a common laboratory oven yields charcoal.

PubMed

Arnal, Pablo Maximiliano

2015-01-01

Charcoals have been widely used by scientist to research the removal of contaminants from water and air. One key feature of charcoal is that it keeps macropores from the parent material - though anisotropically contracted - and can even develop meso- and micropores. However, the controlled thermochemical conversion of biomass into charcoal at laboratory scale normally requires special setups which involve either vacuum or inert gas. Those setups may not be affordable in research groups or educational institutions where the research of charcoals would be highly welcome. In this work, I propose a simple and effective method to steer the thermochemical process that converts sunflower hulls (SFH) into charcoal with basic laboratory resources. The carbonization method: •Place SFH in an airtight aluminum envelope.•Thermally treat SFH within the envelope in a common laboratory oven.•Open the envelope to obtain the carbonized sunflower hulls.

Low-buoyancy thermochemical plumes resolve controversy of classical mantle plume concept

NASA Astrophysics Data System (ADS)

Dannberg, Juliane; Sobolev, Stephan V.

2015-04-01

The Earth's biggest magmatic events are believed to originate from massive melting when hot mantle plumes rising from the lowermost mantle reach the base of the lithosphere. Classical models predict large plume heads that cause kilometre-scale surface uplift, and narrow (100 km radius) plume tails that remain in the mantle after the plume head spreads below the lithosphere. However, in many cases, such uplifts and narrow plume tails are not observed. Here using numerical models, we show that the issue can be resolved if major mantle plumes contain up to 15-20% of recycled oceanic crust in a form of dense eclogite, which drastically decreases their buoyancy and makes it depth dependent. We demonstrate that, despite their low buoyancy, large enough thermochemical plumes can rise through the whole mantle causing only negligible surface uplift. Their tails are bulky (>200 km radius) and remain in the upper mantle for 100 millions of years.

An evaluation of tannery industry wastewater treatment sludge gasification by artificial neural network modeling.

PubMed

Ongen, Atakan; Ozcan, H Kurtulus; Arayıcı, Semiha

2013-12-15

This paper reports on the calorific value of synthetic gas (syngas) produced by gasification of dewatered sludge derived from treatment of tannery wastewater. Proximate and ultimate analyses of samples were performed. Thermochemical conversion alters the chemical structure of the waste. Dried air was used as a gasification agent at varying flow rates, which allowed the feedstock to be quickly converted into gas by means of different heterogeneous reactions. A lab-scale updraft fixed-bed steel reactor was used for thermochemical conversion of sludge samples. Artificial neural network (ANN) modeling techniques were used to observe variations in the syngas related to operational conditions. Modeled outputs showed that temporal changes of model predictions were in close accordance with real values. Correlation coefficients (r) showed that the ANN used in this study gave results with high sensitivity. Copyright © 2013 Elsevier B.V. All rights reserved.

Technical challenges and future direction for high-efficiency metal hydride thermal energy storage systems

NASA Astrophysics Data System (ADS)

Ward, Patrick A.; Corgnale, Claudio; Teprovich, Joseph A.; Motyka, Theodore; Hardy, Bruce; Sheppard, Drew; Buckley, Craig; Zidan, Ragaiy

2016-04-01

Recently, there has been increasing interest in thermal energy storage (TES) systems for concentrated solar power (CSP) plants, which allow for continuous operation when sunlight is unavailable. Thermochemical energy storage materials have the advantage of much higher energy densities than latent or sensible heat materials. Furthermore, thermochemical energy storage systems based on metal hydrides have been gaining great interest for having the advantage of higher energy densities, better reversibility, and high enthalpies. However, in order to achieve higher efficiencies desired of a thermal storage system by the US Department of Energy, the system is required to operate at temperatures >600 °C. Operation at temperatures >600 °C presents challenges including material selection, hydrogen embrittlement and permeation of containment vessels, appropriate selection of heat transfer fluids, and cost. Herein, the technical difficulties and proposed solutions associated with the use of metal hydrides as TES materials in CSP applications are discussed and evaluated.

Reassessment of the OHZ process for the thermochemical decomposition of water. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Findl, E.; Kulesa, F.; Strickland, G.

1983-08-01

A two-step thermochemical process to sequentially produce hydrogen and oxygen from water by the use of a cation-exchanged zeolite, cycled over a temperature range of 25/sup 0/ to 600/sup 0/C, was reassessed at Brookhaven National Laboratory (BNL). Based on the work of Kasai and Bishop (Union Carbide Corp., 1976), C.C.S. Associates (CCSA) performed a preliminary plant-design study for the OHZ (oxygen-hydrogen-zeolite) process, and was responsible for a few laboratory tests of the zeolite. The results of the BNL's more detailed studies showed that although the thermochemical phenomenon is valid, it is neither practical nor a cost-effective method of producing hydrogenmore » from water. Experimental findings were based on tests of indium-exchanged mordenite zeolite (10 grams, as powder) without carrier gas. The cost reassessment, which was made without using any of BNL's experimental data, showed that the hydrogen costs projected by CCSA were low by a factor of about six (2-h cycle time). The corrected costs, $46 to 50/10/sup 6/ Btu H/sub 2/, are about twice those predicted for electrolytic hydrogen ($24/10/sup 6/ Btu). Corrected costs for a cycle time of 4 hours were $54 to 58/10/sup 6/ Btu. This reassessment, which is based on a realistic review of CCSA's preliminary process design, has shown that the corrected costs projected for OHZ hydrogen are so high that no further consideration should be given to development of the concept. 6 references, 14 figures, 6 tables.« less

Thermochemical pretreatment of lignocellulose residues: assessment of the effect on operational conditions and their interactions on the characteristics of leachable fraction.

PubMed

Vásquez, Denisse; Contreras, Elsa; Palma, Carolyn; Carvajal, Andrea

2015-01-01

Annually, large amounts of agricultural residues are produced in Chile, which can be turned into a good opportunity to diversify the energy matrix. These residues have a slow hydrolysis stage during anaerobic digestion; therefore, the application of a pretreatment seems to be an alternative to improve the process. This work focused on applying a thermochemical pretreatment with NaOH on two lignocellulosic residues. The experiments were performed according to a 2(4) factorial design. The factors studied in a 2(4) factorial design were: temperature (60 and 120 °C), pretreatment time (10 and 30 minutes), NaOH dose (2 and 4%), and residue size (<1 and 1-3 mm for wheat straw; 1-5 and 5-10 mm for corn stover). The analyzed response variables were the solubilization of organic matter, and the biodegradability of the lignocellulose hydrolysate. The statistical analysis of the data allowed the identification of the experimental conditions that maximized solubilization of organic matter and biodegradability. The main results showed that more aggressive experimental conditions could increase the breaking down of the structure; in addition, the time of pretreatment was not significant. Conversely, the less aggressive experimental conditions, regarding regent dosage and downsizing, favored the release of biodegradable organic matter. The main conclusion of this study was the identification of the operational conditions of the thermochemical pretreatment that promote maximum biogas production, which was caused due to the solubilization of a large amount of organic matter, but not because of the increase in biodegradability of the released organic matter.

Characterisation of chemical composition and energy content of green waste and municipal solid waste from Greater Brisbane, Australia.

PubMed

Hla, San Shwe; Roberts, Daniel

2015-07-01

The development and deployment of thermochemical waste-to-energy systems requires an understanding of the fundamental characteristics of waste streams. Despite Australia's growing interest in gasification of waste streams, no data are available on their thermochemical properties. This work presents, for the first time, a characterisation of green waste and municipal solid waste in terms of chemistry and energy content. The study took place in Brisbane, the capital city of Queensland. The municipal solid waste was hand-sorted and classified into ten groups, including non-combustibles. The chemical properties of the combustible portion of municipal solid waste were measured directly and compared with calculations made based on their weight ratios in the overall municipal solid waste. The results obtained from both methods were in good agreement. The moisture content of green waste ranged from 29% to 46%. This variability - and the tendency for soil material to contaminate the samples - was the main contributor to the variation of samples' energy content, which ranged between 7.8 and 10.7MJ/kg. The total moisture content of food wastes and garden wastes was as high as 70% and 60%, respectively, while the total moisture content of non-packaging plastics was as low as 2.2%. The overall energy content (lower heating value on a wet basis, LHVwb) of the municipal solid waste was 7.9MJ/kg, which is well above the World Bank-recommended value for utilisation in thermochemical conversion processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhancing anaerobic digestibility and phosphorus recovery of dairy manure through microwave-based thermochemical pretreatment.

PubMed

Jin, Ying; Hu, Zhenhu; Wen, Zhiyou

2009-08-01

Anaerobic digestion and struvite precipitation are two effective ways of treating dairy manure for recovering biogas and phosphorus. Anaerobic digestion of dairy manure is commonly limited by slow fiber degradation, while struvite precipitation is limited by the availability of orthophosphate. The aim of this work is to study the possibility of using microwave-based thermochemical pretreatment to simultaneously enhance manure anaerobic digestibility (through fiber degradation) and struvite precipitation (through phosphorus solubilization). Microwave heating combined with different chemicals (NaOH, CaO, H(2)SO(4), or HCl) enhanced solubilization of manure and degradation of glucan/xylan in dairy manure. However, sulfuric acid-based pretreatment resulted in a low anaerobic digestibility, probably due to the sulfur inhibition and Maillard side reaction. The pretreatments released 20-40% soluble phosphorus and 9-14% ammonium. However, CaO-based pretreatment resulted in lower orthophosphate releases and struvite precipitation efficiency as calcium interferes with phosphate to form calcium phosphate. Collectively, microwave heating combined with NaOH or HCl led to a high anaerobic digestibility and phosphorus recovery. Using these two chemicals, the performance of microwave- and conventional-heating in thermochemical pretreatment was further compared. The microwave heating resulted in a better performance in terms of COD solubilization, glucan/xylan reduction, phosphorus solubilization and anaerobic digestibility. Lastly, temperature and heating time used in microwave treatment were optimized. The optimal values of temperature and heating time were 147 degrees C and 25.3 min for methane production, and 135 degrees C and 26 min for orthophosphate release, respectively.

Thermochemical Processes | Bioenergy | NREL

Science.gov Websites

model catalysts appear on a montage of images of wood chips, liquid gasoline, a gas tanker truck, and a , pipes, and hoses, pouring a liquid from a large hose into a bucket. Integration, Scale-Up, and Piloting

Application of Metal Catalysts for High Selectivity of Glycerol Conversion to Alcohols

DOT National Transportation Integrated Search

2010-11-01

The objective of this project is to determine the applicability of metal-based catalysts and optimize the process conditions for thermochemically producing primary alcohols. Metal catalysts were evaluated for their selectivities for producing alcohol...

A Model for Earth's Mantle Dynamic History for The Last 500 Ma and Its Implications for Continental Vertical Motions and Geomagnetism

NASA Astrophysics Data System (ADS)

Zhong, S.; Olson, P.; Zhang, N.

2012-12-01

Seismic tomography studies indicate that the Earth's mantle structure is characterized by African and Pacific seismically slow velocity anomalies (i.e., thermochemical piles) and circum Pacific seismically fast anomalies (i.e., degree 2) in the lower mantle. Mantle convection calculations including plate motion history for the last 120 Ma suggest that these degree 2 thermochemical structures result from plate subduction history (e.g., McNamara and Zhong, 2005). Given the important controls of mantle structure and dynamics on surface tectonics and volcanism and geodynamo in the core, an important question is the long-term evolution of mantle structures, for example, was the mantle structure in the past similar to the present-day's degree 2 structure, or significantly different from the present day? To address this question, we constructed a proxy model of plate motions for the African hemisphere for the last 450 Ma using the paleogeographic reconstruction of continents constrained by paleomagnetic and geological observations (e.g., Pangea assembly and breakup). Coupled with assumed oceanic plate motions for the Pacific hemisphere before 120 Ma, this proxy model for the plate motion history is used in three dimensional spherical models of mantle convection to study the evolution of mantle structure since the Early Paleozoic. Our model calculations reproduce well the present day degree 2 mantle structure including the African and Pacific thermochemical piles, and present-day surface heat flux, bathymetry and dynamic topography. Our results suggest that while the mantle in the African hemisphere before the assembly of Pangea is dominated by the cold downwelling structure resulting from plate convergence between Gondwana and Laurussia, it is unlikely that the bulk of the African superplume structure can be formed before ˜230 Ma. Particularly, the last 120 Ma plate motion plays an important role in generating the African thermochemical pile. We reconstruct temporal evolution of the surface and CMB heat fluxes and continental vertical motions since the Paleozoic. The predicted vertical motion histories for the Slave and Kaapvaal cratons are consistent with those inferred from thermochronology studies. The predicted CMB heat fluxes were used as time-dependent boundary conditions for geodynamo simulations. And the geodynamo modelling shows that the time-dependent CMB heat fluxes may explain to the first order the frequencies of geomagnetic polarity reversals (e.g., superchrons).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fitzpatrick, Stephen W.

This project involved a three-year program managed by BioMetics, Inc. (Waltham, MA) to demonstrate the commercial feasibility of Biofine thermochemical process technology for conversion of cellulose-containing wastes or renewable materials into levulinic acid, a versatile platform chemical. The program, commencing in October 1995, involved the design, procurement, construction and operation of a plant utilizing the Biofine process to convert 1 dry ton per day of paper sludge waste. The plant was successfully designed, constructed, and commissioned in 1997. It was operated for a period of one year on paper sludge from a variety of source paper mills to collect datamore » to verify the design for a commercial scale plant. Operational results were obtained for four different feedstock varieties. Stable, continuous operation was achieved for two of the feedstocks. Continuous operation of the plant at demonstration scale provided the opportunity for process optimization, development of operational protocols, operator training and identification of suitable materials of construction for scale up to commercial operation . Separated fiber from municipal waster was also successfully processed. The project team consisted of BioMetics Inc., Great Lakes Chemical Corporation (West Lafayette, IN), and New York State Energy Research and Development Authority (Albany, NY).« less

Thermal barrier coating life-prediction model development

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Neumann, J.

1985-01-01

Life predictions are made for two types of strain-tolerant and oxidation-resistant Thermal Barrier Coating (TBC) systems produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma spray (LPPS) applied oxidation-resistant NiCrAlY bond coating and an air-plasma-sprayed yttria (8 percent) partially stabilized zirconia insulative layer, is applied by both Chromalloy and Klock. The second type of TBC is applied by the electron-beam/physical vapor deposition process by Temescal. Thermomechanical and thermochemical testing of the program TBCs is in progress. A number of the former tests has been completed. Fracture mechanics data for the Chromalloy plasma-sprayed TBC system indicate that the cohesive toughness of the zirconia layer is increased by thermal cycling and reduced by high temperature exposure at 1150 C. Eddy current technology feasibility has been established with respect to nondestructively measuring zirconia layer thickness of a TBC system. High pressure turbine blades have been coated with program TBC systems for a piggyback test in a TFE731-5 turbofan factory engine test. Data from this test will be used to validate the TBC life models.

Thermochemical Properties of the Lattice Oxygen in W,Mn-Containing Mixed Oxide Catalysts for the Oxidative Coupling of Methane

NASA Astrophysics Data System (ADS)

Lomonosov, V. I.; Gordienko, Yu. A.; Sinev, M. Yu.; Rogov, V. A.; Sadykov, V. A.

2018-03-01

Mixed NaWMn/SiO2 oxide, samples containing individual components (Na, W, Mn) and their double combinations (Na-W, Na-Mn, W-Mn) supported on silica were studied by temperature programmed reduction (TPR) and desorption (TPD), and heat flow calorimetry during their reoxidation with molecular oxygen in pulse mode. The NaWMn/SiO2 mixed oxide was shown to contain two different types of reactive lattice oxygen. The weakly-bonded oxygen can be reversibly released from the oxide in a flow of inert gas in the temperature range of 575‒900°C, while the strongly-bonded oxygen can be removed during the reduction of the sample with hydrogen at 700-900°C. The measured thermal effect of oxygen consumption for these two oxygen forms are 185 and 350 kJ/mol, respectively. The amount of oxygen removed at reduction ( 443 μmol/g) considerably exceeded the amount desorbed in an inert gas flow ( 56 μmol/g). The obtained results suggest that the reversible oxygen desorption is due to the redox process in which manganese ions are involved, while during the temperature programmed reduction, mainly oxygen bonded with tungsten is removed.

Thermogravimetric characterization of irrigated bermudagrass as a combustion feedstock

USDA-ARS?s Scientific Manuscript database

The bioenergy production industry can benefit from a greater understanding of potential differences among the various feedstock materials and production influences on thermochemical conversion processes such as combustion. The thermal degradation of biomass during combustion can quickly be assessed ...

Biochar elemental composition and factors influencing nutrient retention

USDA-ARS?s Scientific Manuscript database

Biochar is the carbonaceous solid byproduct of the thermochemical conversion of a carbon-bearing organic material, commonly high in cellulose, hemicelluloses, or lignin content, for the purposes of carbon sequestration and storage. More specifically, the thermal conversion process known as pyrolysi...

Char from sugarcane bagasse

USDA-ARS?s Scientific Manuscript database

Unused sugarcane bagasse represents an underutilized resource in sugarcane growing regions of the world. This is a renewable resource that can be used in a thermochemical process to create chars, which could be incorporated back into agricultural activities. The practice is likely to improve soil ...

Do yield and quality of big bluestem and switchgrass feedstock decline over winter?

USDA-ARS?s Scientific Manuscript database

Switchgrass (Panicum virgatum L.) and big bluestem (Andropogon gerdardii Vitman) are potential bioenergy feedstocks for thermochemical platforms. Feedstock storage, fall harvest constraints, and environmental benefits provided by perennials are rationales for developing localized perennial feedstock...

Synthesis of sustainable lubricant enhancer from wet hydrolyzed solids

USDA-ARS?s Scientific Manuscript database

Lignocellulosic ethanol biorefineries offer a sustainable way to produce alternative transportation fuel and provide fiber and biomaterial. However, the lignin fraction remains underutilized in the absence of the development of high value products. Despite its resilience to decomposition, thermochem...

Chemistry of Earth's Putative Steam Atmosphere

NASA Astrophysics Data System (ADS)

Fegley, B.; Schaefer, L.

2007-12-01

The concept of a steam atmosphere generated by impact devolatilization of planetesimals accreted during Earth's formation is over 20 years old (Matsui and Abe, 1986; Lange and Ahrens, 1982). Surprisingly, with the possible exception of a few qualitative remarks, no one has critically assessed this scenario. We use thermochemical equilibrium and, where relevant, thermochemical kinetic calculations to model the chemistry of the "steam" atmosphere produced by impact volatilization of different types of accreting material. We present results for our nominal conditions (1500 K, total P = 100 bar). We also studied the effects of variable temperature and total pressure. The composition of the accreting material is modeled using average compositions of the Orgueil CI chondrite, the Murchison CM2 chondrite, the Allende CV3 chondrite, average ordinary (H, L, LL) chondrites, and average enstatite (EH, EL) chondrites. The major gases released from CI and CM chondritic material are H2O, CO2, H2, H2S, CO, CH4, and SO2 in decreasing order of abundance. About 10% of the atmosphere is CO2. The major gases released from CV chondritic material are CO2, H2O, CO, H2, and SO2 in decreasing order of abundance. About 20% of the total atmosphere is steam. The major gases released from average ordinary chondritic material are H2, CO, H2O, CO2, CH4, H2S, and N2 in decreasing order of abundance. The "steam" atmosphere is predominantly H2 + CO with steam being about 10% of the total atmosphere. The major gases released from EH chondritic material are H2, CO, H2O, CO2, N2, and CH4 in decreasing order of abundance. The "steam" atmosphere is predominantly H2 + CO with about 10% of the total atmosphere as steam. This work was supported by the NASA Astrobiology and Origins Programs.

Comprehensive Assessment of Composition and Thermochemical Variability by High Resolution GC/QToF-MS and the Advanced Distillation-Curve Method as a Basis of Comparison for Reference Fuel Development.

PubMed

Lovestead, Tara M; Burger, Jessica L; Schneider, Nico; Bruno, Thomas J

2016-12-15

Commercial and military aviation is faced with challenges that include high fuel costs, undesirable emissions, and supply chain insecurity that result from the reliance on petroleum-based feedstocks. The development of alternative gas turbine fuels from renewable resources will likely be part of addressing these issues. The United States has established a target for one billion gallons of renewable fuels to enter the supply chain by 2018. These alternative fuels will have to be very similar in properties, chemistry, and composition to existing fuels. To further this goal, the National Jet Fuel Combustion Program (a collaboration of multiple U.S. agencies under the auspices of the Federal Aviation Administration, FAA) is coordinating measurements on three reference gas turbine fuels to be used as a basis of comparison. These fuels are reference fuels with certain properties that are at the limits of experience. These fuels include a low viscosity, low flash point, high hydrogen content "best case" JP-8 (POSF 10264) fuel, a relatively high viscosity, high flash point, low hydrogen content "worst case" JP-5 (POSF 10259) fuel, and a Jet-A (POSF 10325) fuel with relatively average properties. A comprehensive speciation of these fuels is provided in this paper by use of high resolution gas chromatography/quadrupole time-of-flight - mass spectrometry (GC/QToF-MS), which affords unprecedented resolution and exact molecular formula capabilities. The volatility information as derived from the measurement of the advanced distillation curve temperatures, T k and T h , provides an approximation of the vapor liquid equilibrium and examination of the composition channels provides detailed insight into thermochemical data. A comprehensive understanding of the compositional and thermophysical data of gas turbine fuels is required not only for comparison but also for modeling of such complex mixtures, which will, in turn, aid in the development of new fuels with the goals of diversified feedstocks, decreased pollution, and increased efficiency.

Impact of Technology and Feedstock Choice on the Environmental Footprint of Biofuels

NASA Astrophysics Data System (ADS)

Schultz, P. B.; Dodder, R. S.

2012-12-01

The implementation of the U.S. Renewable Fuel Standard program (RFS2) has led to a dramatic shift in the use of biofuel in the U.S. transportation system over the last decade. To satisfy this demand, the production of U.S. corn-based ethanol has grown rapidly, with an average increase of over 25% annually from 2002 to 2010. RFS2 requires a similarly steep increase in the production of advanced biofuels, such as cellulosic ethanol. Unlike corn-based ethanol, which is derived from the biochemical fermentation of sugars in wet and dry mills, it is likely that a more diverse suite of technologies will need to be developed to be able to meet the advanced biofuel RFS2 targets, including biochemical as well as thermochemical (e.g., gasification and pyrolysis) approaches. Rather than relying on energy crops, a potential advantage of thermochemical approaches is the ability to use a wider variety of feedstocks, including municipal solid waste and wood waste. In this work, we conduct a system-level analysis to understand how technology and feedstock choice can impact the environmental footprint of biofuels in the U.S. We use a least-cost optimization model of the U.S. energy system to account for interactions between various components of the energy system: industrial, transportation, electric, and residential/commercial sectors. The model was used to understand the scale of feedstock demand required from dedicated energy crops, as well as other biomass feedstocks, in order to meet the RFS2 mandate. On a regional basis, we compare the overall water-consumption and land requirements for biofuels production given a suite of liquid-fuel production technologies. By considering a range of scenarios, we examine how the use of various feedstocks (e.g., agricultural residues, wood wastes, mill residues and municipal wastes) can be used to off-set environmental impacts as compared to relying solely on energy crops.

Hydrothermal carbonization: modeling, final properties design and applications: a review

USDA-ARS?s Scientific Manuscript database

Active research on biomass hydrothermal carbonization (HTC) continues to demonstrate its advantages over other thermochemical processes, in particular the interesting benefits associated with carbonaceous solid products called hydrochar (HC). The areas of applications of HC range from biofuel to dop...

Growing perennial forages for biomass

USDA-ARS?s Scientific Manuscript database

Recent attention given to converting biomass into ethanol to fuel cars and trucks or burning it to generate electricity has captured society’s interest. There are three main routes for converting biomass into usable forms of energy or other chemical end products: (i) biochemical, (ii) thermochemical...

Thermochemical Analysis of Neutralization Reactions: An Introductory Discovery Experiment

ERIC Educational Resources Information Center

Mills, Kenneth V.; Gullmette, Louise W.

2007-01-01

The article describes a new discovery experiment that uses thermodynamical analysis to study neutralization reactions based on neutralization of citric acid. The experiment would be able to reinforce students' understanding of stoichiometry and allow for the discovery of basic concepts of thermochemistry.

Dairy manure biochar as a phosphorus fertilizer

USDA-ARS?s Scientific Manuscript database

Future manure management practices will need to remove large amounts of organic waste as well as harness energy to generate value-added products. Manures can be processed using thermochemical conversion technologies to generate a solid product called biochar. Dairy manure biochars contain sufficient...

Hydrothermal carbonization of animal manures: Processes and energetics

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is an emerging technology for thermochemically converting biomass and waste materials into value-added carbonaceous char called hydrochar. HTC is well suited to manage wet feedstocks streams because pre-drying prior to processing is not required as with gasification...

Selected global examples of cellulosic cropping system trends

USDA-ARS?s Scientific Manuscript database

Plant biomass has been recognized globally as an important link to a sustainable energy future because it can be grown universally and converted into liquid transportation fuels or other material through biochemical, thermochemical, or catalytic conversion processes. A key challenge is that cellulos...

A Streamline-Upwind Petrov-Galerkin Finite Element Scheme for Non-Ionized Hypersonic Flows in Thermochemical Nonequilibrium

NASA Technical Reports Server (NTRS)

Kirk, Benjamin S.; Bova, Stephen W.; Bond, Ryan B.

2011-01-01

Presentation topics include background and motivation; physical modeling including governing equations and thermochemistry; finite element formulation; results of inviscid thermal nonequilibrium chemically reacting flow and viscous thermal equilibrium chemical reacting flow; and near-term effort.

Energy conversion and storage program

NASA Astrophysics Data System (ADS)

Cairns, E. J.

1992-03-01

The Energy Conversion and Storage Program applies chemistry and materials science principles to solve problems in: (1) production of new synthetic fuels; (2) development of high-performance rechargeable batteries and fuel cells; (3) development of advanced thermochemical processes for energy conversion; (4) characterization of complex chemical processes; and (5) application of novel materials for energy conversion and transmission. Projects focus on transport-process principles, chemical kinetics, thermodynamics, separation processes, organic and physical chemistry, novel materials, and advanced methods of analysis. Electrochemistry research aims to develop advanced power systems for electric vehicle and stationary energy storage applications. Topics include identification of new electrochemical couples for advanced rechargeable batteries, improvements in battery and fuel-cell materials, and the establishment of engineering principles applicable to electrochemical energy storage and conversion. Chemical Applications research includes topics such as separations, catalysis, fuels, and chemical analyses. Included in this program area are projects to develop improved, energy-efficient methods for processing waste streams from synfuel plants and coal gasifiers. Other research projects seek to identify and characterize the constituents of liquid fuel-system streams and to devise energy-efficient means for their separation. Materials Applications research includes the evaluation of the properties of advanced materials, as well as the development of novel preparation techniques. For example, the use of advanced techniques, such as sputtering and laser ablation, are being used to produce high-temperature superconducting films.

Thermal barrier coating life-prediction model development

NASA Technical Reports Server (NTRS)

Strangman, T. E.; Neumann, J.; Liu, A.

1986-01-01

The program focuses on predicting the lives of two types of strain-tolerant and oxidation-resistant thermal barrier coating (TBC) systems that are produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma-spray (LPPS) or an argon shrouded plasma-spray (ASPS) applied oxidation resistant NiCrAlY or (CoNiCrAlY) bond coating and an air-plasma-sprayed yttria partially stabilized zirconia insulative layer, is applied by both Chromalloy, Klock, and Union Carbide. The second type of TBS is applied by the electron beam-physical vapor deposition (EB-PVD) process by Temescal. The second year of the program was focused on specimen procurement, TMC system characterization, nondestructive evaluation methods, life prediction model development, and TFE731 engine testing of thermal barrier coated blades. Materials testing is approaching completion. Thermomechanical characterization of the TBC systems, with toughness, and spalling strain tests, was completed. Thermochemical testing is approximately two-thirds complete. Preliminary materials life models for the bond coating oxidation and zirconia sintering failure modes were developed. Integration of these life models with airfoil component analysis methods is in progress. Testing of high pressure turbine blades coated with the program TBS systems is in progress in a TFE731 turbofan engine. Eddy current technology feasibility was established with respect to nondestructively measuring zirconia layer thickness of a TBC system.

Thermochemical Modeling of Nonequilibrium Oxygen Flows

NASA Astrophysics Data System (ADS)

Neitzel, Kevin Joseph

The development of hypersonic vehicles leans heavily on computational simulation due to the high enthalpy flow conditions that are expensive and technically challenging to replicate experimentally. The accuracy of the nonequilibrium modeling in the computer simulations dictates the design margin that is required for the thermal protection system and flight dynamics. Previous hypersonic vehicles, such as Apollo and the Space Shuttle, were primarily concerned with re-entry TPS design. The strong flow conditions of re-entry, involving Mach numbers of 25, quickly dissociate the oxygen molecules in air. Sustained flight, hypersonic vehicles will be designed to operate in Mach number ranges of 5 to 10. The oxygen molecules will not quickly dissociate and will play an important role in the flow field behavior. The development of nonequilibrium models of oxygen is crucial for limiting modeling uncertainty. Thermochemical nonequilibrium modeling is investigated for oxygen flows. Specifically, the vibrational relaxation and dissociation behavior that dominate the nonequilibrium physics in this flight regime are studied in detail. The widely used two-temperature (2T) approach is compared to the higher fidelity and more computationally expensive state-to-state (STS) approach. This dissertation utilizes a wide range of rate sources, including newly available STS rates, to conduct a comprehensive study of modeling approaches for hypersonic nonequilibrium thermochemical modeling. Additionally, the physical accuracy of the computational methods are assessed by comparing the numerical results with available experimental data. The numerical results and experimental measurements present strong nonequilibrium, and even non-Boltzmann behavior in the vibrational energy mode for the sustained hypersonic flight regime. The STS approach is able to better capture the behavior observed in the experimental data, especially for stronger nonequilibrium conditions. Additionally, a reduced order model (ROM) modification to the 2T model is developed to improve the capability of the 2T approach framework.

A solar receiver-storage modular cascade based on porous ceramic structures for hybrid sensible/thermochemical solar energy storage

NASA Astrophysics Data System (ADS)

Agrafiotis, Christos; de Oliveira, Lamark; Roeb, Martin; Sattler, Christian

2016-05-01

The current state-of-the-art solar heat storage concept in air-operated Solar Tower Power Plants is to store the solar energy provided during on-sun operation as sensible heat in porous solid materials that operate as recuperators during off-sun operation. The technology is operationally simple; however its storage capacity is limited to 1.5 hours. An idea for extending this capacity is to render this storage concept from "purely" sensible to "hybrid" sensible/ thermochemical one, via coating the porous heat exchange modules with oxides of multivalent metals for which their reduction/oxidation reactions are accompanied by significant heat effects, or by manufacturing them entirely of such oxides. In this way solar heat produced during on-sun operation can be used (in addition to sensibly heating the porous solid) to power the endothermic reduction of the oxide from its state with the higher metal valence to that of the lower; the thermal energy can be entirely recovered by the reverse exothermic oxidation reaction (in addition to sensible heat) during off-sun operation. Such sensible and thermochemical storage concepts were tested on a solar-irradiated receiver- heat storage module cascade for the first time. Parametric studies performed so far involved the comparison of three different SiC-based receivers with respect to their capability of supplying solar-heated air at temperatures sufficient for the reduction of the oxides, the effect of air flow rate on the temperatures achieved within the storage module, as well as the comparison of different porous storage media made of cordierite with respect to their sensible storage capacity.

Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

2016-05-01

In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

In vitro thermal profile suitability assessment of acids and bases for thermochemical ablation: underlying principles.

PubMed

Freeman, Laura A; Anwer, Bilal; Brady, Ryan P; Smith, Benjamin C; Edelman, Theresa L; Misselt, Andrew J; Cressman, Erik N K

2010-03-01

To measure and compare temperature changes in a recently developed gel phantom for thermochemical ablation as a function of reagent strength and concentration with several acids and bases. Aliquots (0.5-1 mL) of hydrochloric acid or acetic acid and sodium hydroxide or aqueous ammonia were injected for 5 seconds into a hydrophobic gel phantom. Stepwise increments in concentration were used to survey the temperature changes caused by these reactions. Injections were performed in triplicate, measured with a thermocouple probe, and plotted as functions of concentration and time. Maximum temperatures were reached almost immediately in all cases, reaching 75 degrees C-110 degrees C at the higher concentrations. The highest temperatures were seen with hydrochloric acid and either base. More concentrated solutions of sodium hydroxide tended to mix incompletely, such that experiments at 9 M and higher were difficult to perform consistently. Higher concentrations for any reagent resulted in higher temperatures. Stronger acid and base combinations resulted in higher temperatures versus weak acid and base combinations at the same concentration. Maximum temperatures obtained are in a range known to cause tissue coagulation, and all combinations tested therefore appeared suitable for further investigation in thermochemical ablation. Because of the loss of the reaction chamber shape at higher concentrations of stronger agents, the phantom does not allow complete characterization under these circumstances. Adequate mixing of reagents to maximize heating potential and avoid systemic exposure to unreacted acid and base must be addressed if the method is to be safely employed in tissues. In addition, understanding factors that control lesion shape in a more realistic tissue model will be critical. Copyright 2010 SIR. Published by Elsevier Inc. All rights reserved.

Numerical Prediction of Radiation Measurements Taken in the X2 Facility for Mars and Titan Gas Mixtures

NASA Technical Reports Server (NTRS)

Palmer, Grant; Prabhu, Dinesh; Brandis, Aaron; McIntyre, Timothy J.

2011-01-01

Thermochemical relaxation behind a normal shock in Mars and Titan gas mixtures is simulated using a CFD solver, DPLR, for a hemisphere of 1 m radius; the thermochemical relaxation along the stagnation streamline is considered equivalent to the flow behind a normal shock. Flow simulations are performed for a Titan gas mixture (98% N2, 2% CH4 by volume) for shock speeds of 5.7 and 7.6 km/s and pressures ranging from 20 to 1000 Pa, and a Mars gas mixture (96% CO2, and 4% N2 by volume) for a shock speed of 8.6 km/s and freestream pressure of 13 Pa. For each case, the temperatures and number densities of chemical species obtained from the CFD flow predictions are used as an input to a line-by-line radiation code, NEQAIR. The NEQAIR code is then used to compute the spatial distribution of volumetric radiance starting from the shock front to the point where thermochemical equilibrium is nominally established. Computations of volumetric spectral radiance assume Boltzmann distributions over radiatively linked electronic states of atoms and molecules. The results of these simulations are compared against experimental data acquired in the X2 facility at the University of Queensland, Australia. The experimental measurements were taken over a spectral range of 310-450 nm where the dominant contributor to radiation is the CN violet band system. In almost all cases, the present approach of computing the spatial variation of post-shock volumetric radiance by applying NEQAIR along a stagnation line computed using a high-fidelity flow solver with good spatial resolution of the relaxation zone is shown to replicate trends in measured relaxation of radiance for both Mars and Titan gas mixtures.

Mapping the Earth's thermochemical and anisotropic structure using global surface wave data

NASA Astrophysics Data System (ADS)

Khan, A.; Boschi, L.; Connolly, J. A. D.

2011-01-01

We have inverted global fundamental mode and higher-order Love and Rayleigh wave dispersion data jointly, to find global maps of temperature, composition, and radial seismic anisotropy of the Earth's mantle as well as their uncertainties via a stochastic sampling-based approach. We apply a self-consistent thermodynamic method to systematically compute phase equilibria and physical properties (P and S wave velocity, density) that depend only on composition (in the Na2-CaO-FeO-MgO-Al2O3-SiO2 model system), pressure, and temperature. Our 3-D maps are defined horizontally by 27 different tectonic regions and vertically by a number of layers. We find thermochemical differences between oceans and continents to extend down to ˜250 km depth, with continents and cratons appearing chemically depleted (high magnesium number (Mg #) and Mg/Si ratio) and colder (>100°C) relative to oceans, while young oceanic lithosphere is hotter than its intermediate age and old counterparts. We find what appears to be strong radial S wave anisotropy in the upper mantle down to ˜200 km, while there seems to be little evidence for shear anisotropy at greater depths. At and beneath the transition zone, 3-D heterogeneity is likely uncorrelated with surface tectonics; as a result, our tectonics-based parameterization is tenuous. Despite this weakness, constraints on the gross average thermochemical and anisotropic structure to ˜1300 km depth can be inferred, which appear to indicate that the compositions of the upper (low Mg# and high Mg/Si ratio) and lower mantle (high Mg# and low Mg/Si ratio) might possibly be distinct.

Cyclopentadienone Oxidation Reaction Kinetics and Thermochemistry for the Alcohols, Hydroperoxides, and Vinylic, Alkoxy, and Alkylperoxy Radicals.

PubMed

Yommee, Suriyakit; Bozzelli, Joseph W

2016-01-28

Cyclopentadienone has one carbonyl and two olefin groups resulting in 4n + 2 π-electrons in a cyclic five-membered ring structure. Thermochemical and kinetic parameters for the initial reactions of cyclopentadienone radicals with O2 and the thermochemical properties for cyclopentadienone-hydroperoxides, alcohols, and alkenyl, alkoxy, and peroxy radicals were determined by use of computational chemistry. The CBS-QB3 composite and B3LYP density functional theory methods were used to determine the enthalpies of formation (ΔfH°298) using the isodesmic reaction schemes with several work reactions for each species. Entropy and heat capacity, S°(T) and Cp°(T) (50 K ≤ T ≤ 5000 K) are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations. Standard enthalpies of formation are reported for parent molecules as cyclopentadienone, cyclopentadienone with alcohol, hydroperoxide substituents, and the cyclopentadienone-yl vinylic, alkoxy, and peroxy radicals corresponding to loss of a hydrogen atom from the carbon and oxygen sites. Entropy and heat capacity vs temperature also are reported for the parent molecules and for radicals. The thermochemical analysis shows The R(•) + O2 well depths are deep, on the order of 50 kcal mol(-1), and the R(•) + O2 reactions to RO + O (chain branching products) for cyclopentadienone-2-yl and cyclopentadienone-3-yl have unusually low reaction (ΔHrxn) enthalpies, some 20 or so kcal/mol below the entrance channels. Chemical activation kinetics using quantum RRK analysis for k(E) and master equation for falloff are used to show that significant chain branching as a function of temperature and pressure can occur when these vinylic radicals are formed.

Thermochemical process for the production of hydrogen using chromium and barium compound

DOEpatents

Bamberger, Carlos E.; Richardson, Donald M.

1977-01-25

Hydrogen is produced by a closed cyclic process involving the reduction and oxidation of chromium compounds by barium hydroxide and the hydrolytic disproportionation of Ba.sub.2 CrO.sub.4 and Ba.sub.3 (CrO.sub.4).sub.2.

Mineral nutrient recovery from pyrolysis systems

USDA-ARS?s Scientific Manuscript database

Bioenergy crops such as high-energy sorghum (HES), bioenergy rice, corn stover, and switchgrass can be thermo-chemically converted by pyrolysis to produce bio-oil, synthesis gas from non-condensable gases, and biochar. The biochar fraction can be recycled back to the production field to improve soil...

Contributions of pyrogenic materials on the accumulation of soil organic matter

USDA-ARS?s Scientific Manuscript database

Soil amendment of charcoal co-product (HHVdb as high as coal) from thermochemical waste biomass-to-energy conversion (slow/fast pyrolysis and gasification) has received considerable interests for both contaminated and agricultural lands. Biochar amendment not only increases soil organic carbon cont...

Dielectric properties of biomass and biochar mixtures for bioenergy applications

USDA-ARS?s Scientific Manuscript database

Biomass is an abundant and renewable energy resource, which may be converted into energy-dense products through thermochemical processes such as pyrolysis and gasification. Since microwave heating depends on the dielectric properties of the biomass material, these properties were measured at freque...

Sweet sorghum bagasse for production of biochar

USDA-ARS?s Scientific Manuscript database

Sweet sorghum bagasse is an untapped resourceful carbon-rich material that can be thermochemically converted into value-added biochars. These biochars can be applied to the field as soil amendment for soil health enhancement, improved soil carbon content, water holding capacity, soil drainage and a...

AB INITIO STUDIES ON THERMOCHEMICAL PROPERTIES OF OXIRANE, OXITANE AND OXIRENE. (R824970)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

A general model for techno-economic analysis of CSP plants with thermochemical energy storage systems

NASA Astrophysics Data System (ADS)

Peng, Xinyue; Maravelias, Christos T.; Root, Thatcher W.

2017-06-01

Thermochemical energy storage (TCES), with high energy density and wide operating temperature range, presents a potential solution for CSP plant energy storage. We develop a general optimization based process model for CSP plants employing a wide range of TCES systems which allows us to assess the plant economic feasibility and energy efficiency. The proposed model is applied to a 100 MW CSP plant employing ammonia or methane TCES systems. The methane TCES system with underground gas storage appears to be the most promising option, achieving a 14% LCOE reduction over the current two-tank molten-salt CSP plants. For general TCES systems, gas storage is identified as the main cost driver, while the main energy driver is the compressor electricity consumption. The impacts of separation and different reaction parameters are also analyzed. This study demonstrates that the realization of TCES systems for CSP plants is contingent upon low storage cost and a reversible reaction with proper reaction properties.

Noncatalytic transformation of the crude lipid of ChlorellaI vulgaris into fatty acid methyl ester (FAME) with charcoal via a thermo-chemical process.

PubMed

Kwon, Eilhann E; Jeon, Young Jae; Yi, Haakrho

2013-02-01

The noncatalytic transformation of the crude lipid of Chlorella vulgaris (C. vulgaris) into fatty acid methyl ester (FAME) via a thermo-chemical process was mainly investigated in this work. The crude lipid of C. vulgaris was recovered by means of solvent extraction from C. vulgaris cultivated in a raceway pond. The conventional catalyzed transesterification of crude lipid of C. vulgaris is notably inhibited by the impurities contained in the crude lipid of C. vulgaris. These impurities are inevitably derived from the solvent extraction process for C. vulgaris. However, this work presents the noncatalytic transesterification of microalgal lipid into FAME, which could be an alternative option. For example, the noncatalytic transformation of microalgal lipid into FAME provides evidence that the esterification of free fatty acids (FFAs) and the transesterification of triglycerides can be combined into a single step less susceptible to the impurities and with a high conversion efficiency (∼97%). Copyright © 2012 Elsevier Ltd. All rights reserved.

Characterisation of two-stage ignition in diesel engine-relevant thermochemical conditions using direct numerical simulation

DOE PAGES

Krisman, Alex; Hawkes, Evatt R.; Talei, Mohsen; ...

2016-08-30

With the goal of providing a more detailed fundamental understanding of ignition processes in diesel engines, this study reports analysis of a direct numerical simulation (DNS) database. In the DNS, a pseudo turbulent mixing layer of dimethyl ether (DME) at 400 K and air at 900 K is simulated at a pressure of 40 atmospheres. At these conditions, DME exhibits a two-stage ignition and resides within the negative temperature coefficient (NTC) regime of ignition delay times, similar to diesel fuel. The analysis reveals a complex ignition process with several novel features. Autoignition occurs as a distributed, two-stage event. The high-temperaturemore » stage of ignition establishes edge flames that have a hybrid premixed/autoignition flame structure similar to that previously observed for lifted laminar flames at similar thermochemical conditions. In conclusion, a combustion mode analysis based on key radical species illustrates the multi-stage and multi-mode nature of the ignition process and highlights the substantial modelling challenge presented by diesel combustion.« less

Modelling Behaviour of a Carbon Epoxy Composite Exposed to Fire: Part II—Comparison with Experimental Results

PubMed Central

Tranchard, Pauline; Samyn, Fabienne; Duquesne, Sophie; Estèbe, Bruno; Bourbigot, Serge

2017-01-01

Based on a phenomenological methodology, a three dimensional (3D) thermochemical model was developed to predict the temperature profile, the mass loss and the decomposition front of a carbon-reinforced epoxy composite laminate (T700/M21 composite) exposed to fire conditions. This 3D model takes into account the energy accumulation by the solid material, the anisotropic heat conduction, the thermal decomposition of the material, the gas mass flow into the composite, and the internal pressure. Thermophysical properties defined as temperature dependant properties were characterised using existing as well as innovative methodologies in order to use them as inputs into our physical model. The 3D thermochemical model accurately predicts the measured mass loss and observed decomposition front when the carbon fibre/epoxy composite is directly impacted by a propane flame. In short, the model shows its capability to predict the fire behaviour of a carbon fibre reinforced composite for fire safety engineering. PMID:28772836

Low-buoyancy thermochemical plumes resolve controversy of classical mantle plume concept

PubMed Central

Dannberg, Juliane; Sobolev, Stephan V.

2015-01-01

The Earth's biggest magmatic events are believed to originate from massive melting when hot mantle plumes rising from the lowermost mantle reach the base of the lithosphere. Classical models predict large plume heads that cause kilometre-scale surface uplift, and narrow (100 km radius) plume tails that remain in the mantle after the plume head spreads below the lithosphere. However, in many cases, such uplifts and narrow plume tails are not observed. Here using numerical models, we show that the issue can be resolved if major mantle plumes contain up to 15–20% of recycled oceanic crust in a form of dense eclogite, which drastically decreases their buoyancy and makes it depth dependent. We demonstrate that, despite their low buoyancy, large enough thermochemical plumes can rise through the whole mantle causing only negligible surface uplift. Their tails are bulky (>200 km radius) and remain in the upper mantle for 100 millions of years. PMID:25907970

One-Dimensional Ablation with Pyrolysis Gas Flow Using a Full Newton's Method and Finite Control Volume Procedure

NASA Technical Reports Server (NTRS)

Amar, Adam J.; Blackwell, Ben F.; Edwards, Jack R.

2007-01-01

The development and verification of a one-dimensional material thermal response code with ablation is presented. The implicit time integrator, control volume finite element spatial discretization, and Newton's method for nonlinear iteration on the entire system of residual equations have been implemented and verified for the thermochemical ablation of internally decomposing materials. This study is a continuation of the work presented in "One-Dimensional Ablation with Pyrolysis Gas Flow Using a Full Newton's Method and Finite Control Volume Procedure" (AIAA-2006-2910), which described the derivation, implementation, and verification of the constant density solid energy equation terms and boundary conditions. The present study extends the model to decomposing materials including decomposition kinetics, pyrolysis gas flow through the porous char layer, and a mixture (solid and gas) energy equation. Verification results are presented for the thermochemical ablation of a carbon-phenolic ablator which involves the solution of the entire system of governing equations.

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

NASA Astrophysics Data System (ADS)

Ramenskaya, L. M.; Grishina, E. P.; Kudryakova, N. O.

2018-01-01

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf2 containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around -40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at -91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of -19.3°C forms upon slow cooling.

Thermomechanical and Thermochemical Behavior of a Hafnium-20 Percent Tantalum Alloy. Ph.D. Thesis - North Carolina State Univ., Raleigh

NASA Technical Reports Server (NTRS)

Howell, J. P.

1971-01-01

An investigation was conducted to determine the thermomechanical and thermochemical behavior of a high temperature, oxidation resistant, hafnium-20 percent tantalum alloy. The elastic and shear moduli of this alloy were determined in air up to 1000 C and in vacuum up to 2000 C using a mechanical resonance technique. The internal friction of the alloy was measured up to temperatures greater than 1400 C. Room temperature stress-strain behavior of the oxidized and unoxidized alloy was established. The effect of annealing on the elastic and shear moduli of the extruded rod material was investigated. The martensitic-type phase transformation occurring in the alloy was studied using hot stage metallography and electron microscopy. Static oxidation tests were conducted on the alloy at temperatures from 1000 C to 1700 C with weight gain measurements made as a function of time and temperatures. Surface morphology studies were conducted on the oxide coatings formed at the different temperatures using scanning electron microscopy and X-ray diffraction techniques.

Exploration of the kinetic and thermochemical abilities for the free radical scavenging of two quercetin conformers

NASA Astrophysics Data System (ADS)

Mendoza-Wilson, Ana María; Sotelo-Mundo, Rogerio R.; Balandrán-Quintana, René R.; Glossman-Mitnik, Daniel; Sántiz-gómez, Marco a.; García-orozco, karina D.

2010-09-01

Quercetin has a great antioxidant potential due to its large capacity for free radical scavenging. Although it has been found that conformational changes have a profound effect on its chemical properties, there are few studies where conformation is associated with the antioxidant activity. The aim of this investigation was to explore the kinetic and the thermochemical abilities of two quercetin conformers for the free radical scavenging. Quercetin unhydrate (QUH) and quercetin dihydrate (QDH) conformers were studied employing 2,2-diphenyl-1-picrylhydrazyl (DPPH rad ) as in vitro radical model, and catechol and 4-hexyl-resorcinol as reference systems, for identifying the oxidation products. QDH showed to be most effective under conditions of free radical excess, while QUH was most effective when the flavonoid far exceeds the concentration of free radical. It was found, by means of experimental and computational methods, that 4'-OH, 3-OH and 3'-OH are the main reactive sites of both conformers.

Giant onsite electronic entropy enhances the performance of ceria for water splitting

DOE PAGES

Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.; ...

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Cemore » 4+/Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.« less

On kinetic modelling for solar redox thermochemical H2O and CO2 splitting over NiFe2O4 for H2, CO and syngas production.

PubMed

Dimitrakis, Dimitrios A; Syrigou, Maria; Lorentzou, Souzana; Kostoglou, Margaritis; Konstandopoulos, Athanasios G

2017-10-11

This study aims at developing a kinetic model that can adequately describe solar thermochemical water and carbon dioxide splitting with nickel ferrite powder as the active redox material. The kinetic parameters of water splitting of a previous study are revised to include transition times and new kinetic parameters for carbon dioxide splitting are developed. The computational results show a satisfactory agreement with experimental data and continuous multicycle operation under varying operating conditions is simulated. Different test cases are explored in order to improve the product yield. At first a parametric analysis is conducted, investigating the appropriate duration of the oxidation and the thermal reduction step that maximizes the hydrogen yield. Subsequently, a non-isothermal oxidation step is simulated and proven as an interesting option for increasing the hydrogen production. The kinetic model is adapted to simulate the production yields in structured solar reactor components, i.e. extruded monolithic structures, as well.

Thermochemical characterization of some thermoplastic materials. [flammability and toxicity properties for aircraft interiors

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.; Hilado, C. J.

1977-01-01

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use or being considered for use in aircraft interiors are described. The properties studied included thermomechanical properties such as glass-transition and melt temperature, changes in polymer enthalpy, thermogravimetric analysis in anerobic and oxidative environments, oxygen index, smoke evolution, relative toxicity of the volatile products of pyrolysis, and selected physical properties. The generic polymers evaluated included acrylonitrile butadiene styrene, bisphenol A polycarbonate, 9,9 bis (4-hydroxyphenyl) fluorene polycarbonate-poly (dimethylsiloxane) block polymer, phenolphthalein-bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters, including molding characteristics of some of the advanced polymers, are described. Test results and relative rankings of some of the flammability, smoke, and toxicity properties are presented. Under these test conditions, some of the advanced polymers evaluated were significantly less flammable and toxic than or equivalent to polymers in current use.

High yielding tropical energy crops for bioenergy production: Effects of plant components, harvest years and locations on biomass composition.

PubMed

Surendra, K C; Ogoshi, Richard; Zaleski, Halina M; Hashimoto, Andrew G; Khanal, Samir Kumar

2018-03-01

The composition of lignocellulosic feedstock, which depends on crop type, crop management, locations and plant parts, significantly affects the conversion efficiency of biomass into biofuels and biobased products. Thus, this study examined the composition of different parts of two high yielding tropical energy crops, Energycane and Napier grass, collected across three locations and years. Significantly higher fiber content was found in the leaves of Energycane than stems, while fiber content was significantly higher in the stems than the leaves of Napier grass. Similarly, fiber content was higher in Napier grass than Energycane. Due to significant differences in biomass composition between the plant parts within a crop type, neither biological conversion, including anaerobic digestion, nor thermochemical pretreatment alone is likely to efficiently convert biomass components into biofuels and biobased products. However, combination of anaerobic digestion with thermochemical conversion technologies could efficiently utilize biomass components in generating biofuels and biobased products. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of carbon dioxide on the thermal degradation of lignocellulosic biomass.

PubMed

Kwon, Eilhann E; Jeon, Eui-Chan; Castaldi, Marco J; Jeon, Young Jae

2013-09-17

Using biomass as a renewable energy source via currently available thermochemical processes (i.e., pyrolysis and gasification) is environmentally advantageous owing to its intrinsic carbon neutrality. Developing methodologies to enhance the thermal efficiency of these proven technologies is therefore imperative. This study aimed to investigate the use of CO2 as a reaction medium to increase not only thermal efficiency but also environmental benefit. The influence of CO2 on thermochemical processes at a fundamental level was experimentally validated with the main constituents of biomass (i.e., cellulose and xylan) to avoid complexities arising from the heterogeneous matrix of biomass. For instance, gaseous products including H2, CH4, and CO were substantially enhanced in the presence of CO2 because CO2 expedited thermal cracking behavior (i.e., 200-1000%). This behavior was then universally observed in our case study with real biomass (i.e., corn stover) during pyrolysis and steam gasification. However, further study is urgently needed to optimize these experimental findings.

Anisotropic diamond etching through thermochemical reaction between Ni and diamond in high-temperature water vapour.

PubMed

Nagai, Masatsugu; Nakanishi, Kazuhiro; Takahashi, Hiraku; Kato, Hiromitsu; Makino, Toshiharu; Yamasaki, Satoshi; Matsumoto, Tsubasa; Inokuma, Takao; Tokuda, Norio

2018-04-27

Diamond possesses excellent physical and electronic properties, and thus various applications that use diamond are under development. Additionally, the control of diamond geometry by etching technique is essential for such applications. However, conventional wet processes used for etching other materials are ineffective for diamond. Moreover, plasma processes currently employed for diamond etching are not selective, and plasma-induced damage to diamond deteriorates the device-performances. Here, we report a non-plasma etching process for single crystal diamond using thermochemical reaction between Ni and diamond in high-temperature water vapour. Diamond under Ni films was selectively etched, with no etching at other locations. A diamond-etching rate of approximately 8.7 μm/min (1000 °C) was successfully achieved. To the best of our knowledge, this rate is considerably greater than those reported so far for other diamond-etching processes, including plasma processes. The anisotropy observed for this diamond etching was considerably similar to that observed for Si etching using KOH.

Experimental Studies on Mass Transport of Cadmium-Zinc Telluride by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Palosz, W.; Szofran, F. R.; Lehoczky, S. L.

1995-01-01

Experimental studies on mass transport of ternary compound, Cd(1-x)Zn(x)Te by physical vapor transport (PVT) for source compositions up to X = 0.21 are presented. The effect of thermochemical (temperatures, vapor composition) and other factors (preparation of the source, crystal growth rate, temperature gradient) on composition and composition profiles of the grown crystals were investigated. A steep decrease in the mass flux with an increase in X(crystal) for X less than 0.1, and a difference in composition between the source and the deposited material have been observed. The composition profiles of the crystals were found to depend on the density and pretreatment of the source, and on the temperature gradient in the source zone. The homogeneity of the crystals improves at low undercoolings and/or when an appropriate excess of metal constituents is present in the vapor phase. The experimental results are in good agreement with our thermochemical model of this system.

Mass spectrometer measurements of test gas composition in a shock tunnel

NASA Technical Reports Server (NTRS)

Skinner, K. A.; Stalker, R. J.

1995-01-01

Shock tunnels afford a means of generating hypersonic flow at high stagnation enthalpies, but they have the disadvantage that thermochemical effects make the composition of the test flow different to that of ambient air. The composition can be predicted by numerical calculations of the nozzle flow expansion, using simplified thermochemical models and, in the absence of experimental measurements, it has been necessary to accept the results given by these calculations. This note reports measurements of test gas composition, at stagnation enthalpies up to 12.5 MJ.kg(exp -1), taken with a time-of-flight mass spectrometer. Limited results have been obtained in previous measurements. These were taken at higher stagnation enthalpies, and used a quadruple mass spectrometer. The time-of-flight method was preferred here because it enabled a number of complete mass spectra to be obtained in each test, and because it gives good mass resolution over the range of interest with air (up to 50 a.m.a.).

Modelling Behaviour of a Carbon Epoxy Composite Exposed to Fire: Part II-Comparison with Experimental Results.

PubMed

Tranchard, Pauline; Samyn, Fabienne; Duquesne, Sophie; Estèbe, Bruno; Bourbigot, Serge

2017-04-28

Based on a phenomenological methodology, a three dimensional (3D) thermochemical model was developed to predict the temperature profile, the mass loss and the decomposition front of a carbon-reinforced epoxy composite laminate (T700/M21 composite) exposed to fire conditions. This 3D model takes into account the energy accumulation by the solid material, the anisotropic heat conduction, the thermal decomposition of the material, the gas mass flow into the composite, and the internal pressure. Thermophysical properties defined as temperature dependant properties were characterised using existing as well as innovative methodologies in order to use them as inputs into our physical model. The 3D thermochemical model accurately predicts the measured mass loss and observed decomposition front when the carbon fibre/epoxy composite is directly impacted by a propane flame. In short, the model shows its capability to predict the fire behaviour of a carbon fibre reinforced composite for fire safety engineering.

Static Thermochemical Model of COREX Melter Gasifier

NASA Astrophysics Data System (ADS)

Srishilan, C.; Shukla, Ajay Kumar

2018-02-01

COREX is one of the commercial smelting reduction processes. It uses the finer size ore and semi-soft coal instead of metallurgical coke to produce hot metal from iron ore. The use of top gas with high calorific value as a by-product export gas makes the process economical and green. The predictive thermochemical model of the COREX process presented here enables rapid computation of process parameters such as (1) required amount of ore, coal, and flux; (2) amount of slag and gas generated; and (3) gas compositions (based on the raw material and desired hot metal quality). The model helps in predicting the variations in process parameters with respect to the (1) degree of metallization and (2) post-combustion ratio for given raw material conditions. In general reduction in coal, flux, and oxygen, the requirement is concomitant with an increase in the degree of metallization and post-combustion ratio. The model reported here has been benchmarked using industrial data obtained from the JSW Steel Plant, India.

Saikrishna Mukkamala | NREL

Science.gov Websites

Saikrishna Mukkamala Saikrishna Mukkamala Researcher IV-Chemical Engineering Saikrishna.Mukkamala thermochemical, biochemical pathways Bio product and fuel characterization Education M.S. Chemical Engineering , University of Maine B.S. Chemical Engineering, JNTU-India Featured Publications S. Mukkamala, M.C. Wheeler

Yannick J. Bomble, Ph.D. | NREL

Science.gov Websites

Yannick.Bomble@nrel.gov | 303-384-7729 Research Interests Development of thermophilic bacteria for improved Quantum chemical calculations for the study of thermochemical properties and processes Affiliated Research ©matiques Superieures, Lycée Faidherbe, Lille, France, 1998 Professional Experience Senior Research

Techno-Economic, Sustainability, and Market Analysis | Bioenergy | NREL

Science.gov Websites

Techno-Economic, Sustainability, and Market Analysis Techno-Economic, Sustainability, and Market Analysis NREL conducts techno-economic analyses (TEAs) for algal biofuels, thermochemical conversion, and agitating the liquid as it flows around. Algal Biofuels Techno-Economic Analysis NREL's Algae Techno

A burner for plasma-coal starting of a boiler

NASA Astrophysics Data System (ADS)

Peregudov, V. S.

2008-04-01

Advanced schemes of a plasma-coal burner with single-and two-stage chambers for thermochemical preparation of fuel are described. The factors causing it becoming contaminated with slag during oil-free starting of a boiler are considered, and methods for preventing this phenomenon are pointed out.

The Thermit Reaction: A Dazzling Thermochemical Demonstration.

ERIC Educational Resources Information Center

Kauffman, George B.

1997-01-01

Describes an outdoor scientific demonstration of metal reduction, a reaction known as the thermit process. Heat from an ignition mixture is required to initiate the reaction, which then becomes self-sustaining. The demonstration provides a dazzling introduction to such fundamental general chemistry topics as oxidation-reduction, metallurgy,…

Should biochar be used in container substrates?

USDA-ARS?s Scientific Manuscript database

Biochar is charred organic matter that remains after a process called pyrolysis. Pyrolysis is a thermochemical decomposition of organic matter. In this process, organic matter is subjected to extremely high temperatures (200 to 800 °C) in the absence of oxygen. The history of biochar use begins i...

Across-phase biomass pyrolysis stoichiometry, energy balance, and product formation kinetics

USDA-ARS?s Scientific Manuscript database

Predictive correlations between reactions occurring in the gas-, liquid- and solid-phases are necessary to economically utilize the thermochemical conversion of agricultural wastes impacting the food, water, and energy nexus. On the basis of an empirical mass balance (99.7%), this study established...

Conversion of sweet sorghum bagasse into value-added biochar

USDA-ARS?s Scientific Manuscript database

Sweet sorghum bagasse is an untapped resourceful carbon-rich material that can be thermochemically converted into value-added biochars. These biochars can be applied to the field as soil amendment for soil health enhancement, improved soil carbon content, water holding capacity, soil drainage and a...

Response of maize germination and growth to HTC filtrate type and concentration

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is a thermochemical treatment process that allows for the conversion of biomass slurries into value added products. The option of using HTC filtrate as a liquid based fertilizer for agricultural crop production was evaluated through germination and plant growth studi...

Evaluation of Brazilian biomasses as potential feedstocks for fuel production via fast pyrolysis

USDA-ARS?s Scientific Manuscript database

The utilization of lignocellulosic materials to generate energy is constantly expanding around the world. In addition to the well-known biofuels such as ethanol and biodiesel, advanced biofuels obtained by thermochemical conversion routes have been explored, including pyrolysis oil, biochar and syng...

Two Multipurpose Thermochemical Experiments for General Chemistry.

ERIC Educational Resources Information Center

Wentworth, R. A. D.

1988-01-01

Describes two experiments designed to provide concepts on the difference between heat and temperature and also bond energy. Investigates both a neutralization experiment and a ligation experiment. Notes inexpensive chemicals are used along with simple equipment. Discusses the sharing of lab results for a single class value. (MVL)

Adam Bratis, Ph.D. | NREL

Science.gov Websites

Sciences & Technology Adam.Bratis@nrel.gov | 303-384-7852 Areas of Expertise Adam Bratis joined the managerial oversight in the areas of biochemical conversion, thermochemical conversion, algal biofuels with 11 years of experience with ExxonMobil in the areas of research and development, corporate

Multiple sulfur isotopes monitor fluid evolution of an Archean orogenic gold deposit

NASA Astrophysics Data System (ADS)

LaFlamme, Crystal; Sugiono, Dennis; Thébaud, Nicolas; Caruso, Stefano; Fiorentini, Marco; Selvaraja, Vikraman; Jeon, Heejin; Voute, François; Martin, Laure

2018-02-01

The evolution of a gold-bearing hydrothermal fluid from its source to the locus of gold deposition is complex as it experiences rapid changes in thermochemical conditions during ascent through the crust. Although it is well established that orogenic gold deposits are generated during time periods of abundant crustal growth and/or reworking, the source of fluid and the thermochemical processes that control gold precipitation remain poorly understood. In situ analyses of multiple sulfur isotopes offer a new window into the relationship between source reservoirs of Au-bearing fluids and the thermochemical processes that occur along their pathway to the final site of mineralisation. Whereas δ34S is able to track changes in the evolution of the thermodynamic conditions of ore-forming fluids, Δ33S is virtually indelible and can uniquely fingerprint an Archean sedimentary reservoir that has undergone mass independent fractionation of sulfur (MIF-S). We combine these two tracers (δ34S and Δ33S) to characterise a gold-bearing laminated quartz breccia ore zone and its sulfide-bearing alteration halo in the (+6 Moz Au) structurally-controlled Archean Waroonga deposit located in the Eastern Goldfields Superterrane of the Yilgarn Craton, Western Australia. Over 250 analyses of gold-associated sulfides yield a δ34S shift from what is interpreted as an early pre-mineralisation phase, with chalcopyrite-pyrrhotite (δ34S = +0.7‰ to +2.9‰) and arsenopyrite cores (δ34S = ∼-0.5‰), to a syn-mineralisation stage, reflected in Au-bearing arsenopyrite rims (δ34S = -7.6‰ to +1.5‰). This shift coincides with an unchanging Δ33S value (Δ33S = +0.3‰), both temporally throughout the Au-hosting hydrothermal sulfide paragenesis and spatially across the Au ore zone. These results indicate that sulfur is at least partially recycled from MIF-S-bearing Archean sediments. Further, the invariant nature of the observed MIF-S signature demonstrates that sulfur is derived from a homogeneous MIF-S-bearing fluid reservoir at depth, rather than being locally sourced at the site of Au precipitation. Finally, by constraining the MIF-S-bearing sulfur source to a fixed reservoir, we are able to display the thermochemical evolution of the ore fluid in δ34S space and capture the abrupt change in oxidation state that causes Au precipitation. Our results highlight the importance of constraining multiple sulfur isotopes in space and time in order to elucidate the source and evolution of any given Au-bearing fluid.

The PM-200 lubrication system

NASA Technical Reports Server (NTRS)

Sliney, Harold E.

1991-01-01

Plasma sprayed composite coating of metal-bonded chromium carbide with additions of silver and thermochemically stable fluorides were previously reported to be lubricative in pin on desk bench tests from room temperature to 900 C. An early coating formulation of this type, designated as PS-200, was successfully tested as a cylinder coating in a Stirling engine at a TRRT of 760 C in a hydrogen atmosphere, and as a backup lubricant for gas bearings to 650 C. A subsequent optimization program has shown that tribological properties are further improved by increasing the solid lubricant content. The improved coating is designated as PS-212. The same powder formulation was used to make free-standing powder metallurgy (PM-212) parts by sintering or hot isostatic pressing. The process is very attractive for making parts that cannot be readily plasma sprayed such as bushings and cylinders that have small bore diameters and/or high length to diameter ratios. The properties of coatings and free-standing parts fabricated from these powders are reviewed.

An experimental determination in Calspan Ludwieg tube of the base environment of the integrated space shuttle vehicle at simulated Mach 4.5 flight conditions (test IH5 of model 19-OTS)

NASA Technical Reports Server (NTRS)

Drzewiecki, R. F.; Foust, J. W.

1976-01-01

A model test program was conducted to determine heat transfer and pressure distributions in the base region of the space shuttle vehicle during simulated launch trajectory conditions of Mach 4.5 and pressure altitudes between 90,000 and 210,000 feet. Model configurations with and without the solid propellant booster rockets were examined to duplicate pre- and post-staging vehicle geometries. Using short duration flow techniques, a tube wind tunnel provided supersonic flow over the model. Simultaneously, combustion generated exhaust products reproduced the gasdynamic and thermochemical structure of the main vehicle engine plumes. Heat transfer and pressure measurements were made at numerous locations on the base surfaces of the 19-OTS space shuttle model with high response instrumentation. In addition, measurements of base recovery temperature were made indirectly by using dual fine wire and resistance thermometers and by extrapolating heat transfer measurements.

Detonation Performance Analyses for Recent Energetic Molecules

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Samuels, Philip; Spangler, Kimberly; Iwaniuk, Daniel; Cornell, Rodger; Baker, Ernest

2017-06-01

Detonation performance analyses were conducted for a number of evolving and potential high explosive materials. The calculations were completed for theoretical maximum densities of the explosives using the Jaguar thermo-chemical equation of state computer programs for performance evaluations and JWL/JWLB equations of state parameterizations. A number of recently synthesized materials were investigated for performance characterizations and comparisons to existing explosives, including TNT, RDX, HMX, and Cl-20. The analytic cylinder model was utilized to establish cylinder and Gurney velocities as functions of the radial expansions of the cylinder for each explosive. The densities and heats of formulation utilized in the calculations are primarily experimental values from Picatinny Arsenal and other sources. Several of the new materials considered were predicted to have enhanced detonation characteristics compared to conventional explosives. In order to confirm the accuracy of the Jaguar and analytic cylinder model results, available experimental detonation and Gurney velocities for representative energetic molecules and their formulations were compared with the corresponding calculated values. Close agreement was obtained with most of the data. Presently at NATO.

Catalytic thermal cracking of postconsumer waste plastics to fuels. 2. Pilot-scale thermochemical conversion

USDA-ARS?s Scientific Manuscript database

Synthetic gasoline and diesel fuels were prepared via catalytic and noncatalytic pyrolysis of waste polyethylene and polypropylene plastics followed by distillation of plastic crude oils. Reaction conditions optimized using a 2 L batch reactor were applied to pilot-scale production of plastic crude ...

Hydrothermal carbonization of municipal solid waste for carbon sequestration and energy generation

USDA-ARS?s Scientific Manuscript database

A fairly new, innovative technique, called hydrothermal carbonization (HTC), has the potential to change the way municipal solid waste (MSW) is managed. HTC is a wet, low temperature (180-350°C), low pressure (in a closed system) thermochemical waste treatment/conversion technology that has been sho...

Heterogeneous Catalysis for Thermochemical Conversion | Bioenergy | NREL

Science.gov Websites

redox Ce-ZrO2 support. This article discusses research findings that appropriately frame the challenges to aid in bridging the findings of theoretical and experimental catalysis research, and transforming zeolite active site design from an empirical endeavor into a more predictable science founded on validated

Pelletizing properties of torrefied spruce

Treesearch

Wolfgang Stelte; Craig Clemons; Jens K. Holm; Anand R. Sanadi; Jesper Ahrenfeldt; Lei Shang; Ulrik B. Henriksen

2011-01-01

Torrefaction is a thermo-chemical conversion process improving the handling, storage and combustion properties of wood. To save storage space and transportation costs, it can be compressed into fuel pellets of high physical and energetic density. The resulting pellets are relatively resistant to moisture uptake, microbiological decay and easy to comminute into small...

Thermo-chemical and biological conversion potential of various biomass feedstocks to ethanol

USDA-ARS?s Scientific Manuscript database

The goal of this study is to evaluate the potential and the economy of producing ethanol from gasification-fermentation of various biomass feedstocks. The biomass feedstocks include winter cover crops (wheat, rye, clover, hairy betch), summer cover crop (sunhemp), chicken litter, and woody biomass. ...

Thermochemical conversion technologies for production of renewable energy and value-added char from animal manures

USDA-ARS?s Scientific Manuscript database

Confined animal feeding operations (CAFOs) in the USA and many other countries have undergone extensive expansions and consolidations for the last few decades. This shift in animal production agriculture toward fewer, but larger operations has created serious environmental concerns in recycling and ...

The Thermochemical Stability of Ionic Noble Gas Compounds.

ERIC Educational Resources Information Center

Purser, Gordon H.

1988-01-01

Presents calculations that suggest stoichiometric, ionic, and noble gas-metal compounds may be stable. Bases calculations on estimated values of electron affinity, anionic radius for the noble gases and for the Born exponents of resulting crystals. Suggests the desirability of experiments designed to prepare compounds containing anionic,…

An investigation of equilibrium concepts

NASA Technical Reports Server (NTRS)

Prozan, R. J.

1982-01-01

A different approach to modeling of the thermochemistry of rocket engine combustion phenomena is presented. The methodology described is based on the hypothesis of a new variational principle applicable to compressible fluid mechanics. This hypothesis is extended to treat the thermochemical behavior of a reacting (equilibrium) gas in an open system.

Reversible and irreversible sorption of agrochemicals in biochar amended soils: synergistic effects of heavy metals

USDA-ARS?s Scientific Manuscript database

Soil amendment of biochar products from thermochemical waste-to-energy conversion (slow/fast pyrolysis and gasification) of biomass has received considerable interests for both contaminated and agricultural sites. Recalcitrant nature of biochar manifests in their decade-long effectiveness in soil a...

Potential heat exchange fluids for use in sulfuric acid vaporizers

NASA Technical Reports Server (NTRS)

Lawson, D. D.; Petersen, G. R.

1981-01-01

A series of liquids have been screened as candidate heat exchange fluids for service in thermochemical cycles that involve the vaporization of sulfuric acid. The required chemical and physical criteria of the liquids is described with the results of some preliminary high temperature test data presented.

Depolymerization of lignin via co-pyrolysis with 1,4-butanediol in a microwave reactor

USDA-ARS?s Scientific Manuscript database

The production of valuable compounds from low cost but abundant residual lignin has proven to be challenging. The lack of effective biochemical lignin depolymerization processes has led many to focus on thermochemical conversion methods. Bench scale microwave pyrolysis of lignin has been performed...

Valorization of guayule as a feedstock for lignocellulosic biorefineries using ammonia fiber expansion (AFEX) pretreatment

USDA-ARS?s Scientific Manuscript database

Natural rubber latex extraction from guayule leaves behind greater than 80% (by weight) of agricultural residue as a feedstock suitable for conversion to biofuels via a thermochemical or biochemical route. Untreated guayule shrub and bagasse (after latex extraction) has shown to be very recalcitrant...

Stabilization of lead and copper by biochar amendments in arms range soils: Influence of biochar characteristics, soil property, and equilibrium conditions

USDA-ARS?s Scientific Manuscript database

Soil amendment of char products (biochar) from thermochemical processing (slow/fast pyrolysis and gasification) of biomass for biofuel production has received considerable interests for contaminant sorption, soil fertilization, and carbon sequestration. Of potential sites for biochar application, h...

Chemical characterization of chars developed from thermochemical treatment of Kentucky bluegrass seed screenings

USDA-ARS?s Scientific Manuscript database

Char produced from the gasification of post-seed harvest Kentucky bluegrass residues could be recycled to a cropping system as a soil amendment if chemical characterization determined that the gasification process had not produced or concentrated deleterious chemical or physical factors that might h...

Impact of two hydrothermal carbonization filtrates on soil greenhouse production

USDA-ARS?s Scientific Manuscript database

Hydrothermal carbonization (HTC) is a thermochemical treatment process that allows for the conversion of wet biomass slurries to new liquid and solid products. A majority of the research to date has focused on the solid HTC product (hydrochar). Less attention has been paid to the utilization of the ...

Thermodynamic properties of zeolites: low-temperature heat capacities and thermodynamic functions for phillipsite and clinoptilolite. Estimates of the thermochemical properties of zeolitic water at low temperature.

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.

1984-01-01

Measured heat capacities between 15 and 305 K and calculated heat capacities, entropies, enthalpy functions and Gibbs energy functions are reported and analysed for phillipsite and clinoptilolite. - J.A.Z.

Hydrogen Production and Delivery | Hydrogen and Fuel Cells | Hydrogen and

Science.gov Websites

degrees Celsius. Ultra-high temperatures are required for thermochemical reaction cycles to produce for the environmentally benign production of hydrogen. Very high reaction rates at these elevated temperatures give rise to very fast reaction rates, which significantly enhance production rates and more than

Compositional and thermal evaluation of lignocellulosic and poultry litter chars via high and low temperature pyrolysis

USDA-ARS?s Scientific Manuscript database

Inorganic elements in biomass feedstocks can influence thermochemical reactions as well as the resultant chars elemental, compositional, and thermal characteristics. Chars were produced using slow pyrolysis at less than 400 and at higher than 500 degree Celsius from sugarcane bagasse, peanut hulls,...

Genetic Resources of Energy Crops: Biological Systems to Combat Climate Change

USDA-ARS?s Scientific Manuscript database

Biological systems are expected to contribute to renewable energy production, help stabilize rising levels of green house gases (GHG), and mitigate the risk of global climate change (GCC). Bioenergy crop plants that function as solar energy collectors and thermo-chemical energy storage systems are t...

Sulfuric Acid and Water: Paradoxes of Dilution

ERIC Educational Resources Information Center

Leenson, I. A.

2004-01-01

On equilibrium properties of aqueous solutions of sulfuric acid, Julius Thomsen has marked that the heat evolved on diluting liquid sulfuric acid with water is a continuous function of the water used, and excluded absolutely the acceptance of definite hydrates as existing in the solution. Information about thermochemical measurement, a discussion…

Transglutaminase-treated conjugation of sodium caseinate and corn fiber gum hydrolysate: Interfacial and dilatational properties

USDA-ARS?s Scientific Manuscript database

The effects of thermochemical hydrolysis of corn fiber gum (CFG) and conjugation of the resulting oligomers with sodium caseinate in presence of transglutaminase was studied. The dynamic interfacial tension at the oil-water interface was studied and the molecular characteristics were determined by h...

Review of chemical-kinetic problems of future NASA missions, II: Mars entries

NASA Technical Reports Server (NTRS)

Park, Chul; Howe, John T.; Jaffe, Richard L.; Candler, Graham V.

1994-01-01

The present work aims to derive a set of thermomechanical relaxation rate parameters and chemical reaction rate coefficients relevant to future interplanetary missions. It also attempts to assess the impact of thermochemical nonequilibrium phenomena on radiative heating rates for the stagnation point of the Martian entry vehicle.

Study of Oxygen Diffusion in Reduced LiNbO3 Crystals

NASA Astrophysics Data System (ADS)

Yatsenko, A. V.; Pritulenko, A. S.; Yagupov, S. V.; Sugak, D. Yu.; Sol'skii, I. M.

2018-03-01

Using the method of impedance spectroscopy and optical density measurements, the diffusion of oxygen in single crystals of lithium niobate of the congruent composition after the reductive thermochemical processing is studied. The parameters describing the diffusion of oxygen in the temperature range 493-693 K are established.

Proceedings of the DOE chemical energy storage and hydrogen energy systems contracts review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Sessions were held on electrolysis-based hydrogen storage systems, hydrogen production, hydrogen storage systems, hydrogen storage materials, end-use applications and system studies, chemical heat pump/chemical energy storage systems, systems studies and assessment, thermochemical hydrogen production cycles, advanced production concepts, and containment materials. (LHK)

Impact Ignition and Combustion Behavior of Amorphous Metal-Based Reactive Composites

NASA Astrophysics Data System (ADS)

Mason, Benjamin; Groven, Lori; Son, Steven

2013-06-01

Recently published molecular dynamic simulations have shown that metal-based reactive powder composites consisting of at least one amorphous component could lead to improved reaction performance due to amorphous materials having a zero heat of fusion, in addition to having high energy densities and potential uses such as structural energetic materials and enhanced blast materials. In order to investigate the feasibility of these systems, thermochemical equilibrium calculations were performed on various amorphous metal/metalloid based reactive systems with an emphasis on commercially available or easily manufactured amorphous metals, such as Zr and Ti based amorphous alloys in combination with carbon, boron, and aluminum. Based on the calculations and material availability material combinations were chosen. Initial materials were either mixed via a Resodyn mixer or mechanically activated using high energy ball milling where the microstructure of the milled material was characterized using x-ray diffraction, optical microscopy and scanning electron microscopy. The mechanical impact response and combustion behavior of select reactive systems was characterized using the Asay shear impact experiment where impact ignition thresholds, ignition delays, combustion velocities, and temperatures were quantified, and reported. Funding from the Defense Threat Reduction Agency (DTRA), Grant Number HDTRA1-10-1-0119. Counter-WMD basic research program, Dr. Suhithi M. Peiris, program director is gratefully acknowledged.

Thermal barrier coating life-prediction model development. Annual report no. 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strangman, T. E.; Neumann, J.; Liu, A.

1986-10-01

The program focuses on predicting the lives of two types of strain-tolerant and oxidation-resistant thermal barrier coating (TBC) systems that are produced by commercial coating suppliers to the gas turbine industry. The plasma-sprayed TBC system, composed of a low-pressure plasma-spray (LPPS) or an argon shrouded plasma-spray (ASPS) applied oxidation resistant NiCrAlY or (CoNiCrAlY) bond coating and an air-plasma-sprayed yttria partially stabilized zirconia insulative layer, is applied by both Chromalloy, Klock, and Union Carbide. The second type of TBS is applied by the electron beam-physical vapor deposition (EB-PVD) process by Temescal. The second year of the program was focused on specimenmore » procurement, TMC system characterization, nondestructive evaluation methods, life prediction model development, and TFE731 engine testing of thermal barrier coated blades. Materials testing is approaching completion. Thermomechanical characterization of the TBC systems, with toughness, and spalling strain tests, was completed. Thermochemical testing is approximately two-thirds complete. Preliminary materials life models for the bond coating oxidation and zirconia sintering failure modes were developed. Integration of these life models with airfoil component analysis methods is in progress. Testing of high pressure turbine blades coated with the program TBS systems is in progress in a TFE731 turbofan engine. Eddy current technology feasibility was established with respect to nondestructively measuring zirconia layer thickness of a TBC system.« less

Life-Cycle Assessment of a Distributed-Scale Thermochemical Bioenergy Conversion System

Treesearch

Hongmei Gu; Richard Bergman

2016-01-01

Expanding bioenergy production from woody biomass has the potential to decrease net greenhouse gas (GHG) emissions and improve the energy security of the United States. Science-based and internationally accepted life-cycle assessment (LCA) is an effective tool for policy makers to make scientifically informed decisions on expanding renewable energy production from...

Biomass Feedstocks | Bioenergy | NREL

Science.gov Websites

publications. Photo of a group of smiling men and women posing in a casual office setting. Thermochemical xylose) from bioconversion of pelleted and non-pelleted corn stover (CS), Switchgrass (SWG), and Hybrid Variety on the x-axis, showing Non-pelleted (yellow) and Pelleted (orange) results for five groups of data

Jack R. Ferrell III | NREL

Science.gov Websites

Jack R. Ferrell III Photo of Jack R. Ferrell III Jack Ferrell Research Engineer Jack.Ferrell @nrel.gov | 303-384-7777 Orcid ID http://orcid.org/0000-0003-3041-8742 Research Interests Jack Ferrell works in the Thermochemical Catalysis Research and Development (R&D) group and manages tasks on

Lignosulfonate-mediated cellulase adsorption: enhanced enzymatic saccharification of lignocellulose through weakening nonproductive binding to lignin

Treesearch

Zhaojiang Wang; JY Zhu; Yingjuan Fu; Menghua Qin; Zhiyong Shao; Jungang Jiang; Fang Yang

2013-01-01

Thermochemical pretreatment of lignocellulose is crucial to bioconversion in the fields of biorefinery and biofuels. However, the enzyme inhibitors in pretreatment hydrolysate make solid substrate washing and hydrolysate detoxification indispensable prior to enzymatic hydrolysis. Sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL) is a relatively...

Biochar: Is it a sustainable solution to dry land agriculture, forest soil reclamation and greenhouse gas mitigation?

USDA-ARS?s Scientific Manuscript database

Biochar is the carbon-rich solid co-product of thermochemical biofuel production, which has been advocated as a soil amendment capable of sequestering carbon while simultaneously improving crop yields and ecosystem sustainability. The recovery of biochar from biofuel production systems and its use a...

Diagnostic and Treatment Innovations for Mass Casualties

DTIC Science & Technology

2016-08-01

measurement * U.S. Customary Units Multiply by International Units Divide by † Length/ Area /Volume inch (in) 2.54 × 10 –2 meter (m) foot...cal) (thermochemical) 4.184 joule (J) Pressure atmosphere (atm) 1.013 250 × 10 5 pascal (Pa) pound force per square inch (psi) 6.984 757 × 10

Use of Biochar from the Pyrolysis of Waste Organic Material as a Soil Amendment

USDA-ARS?s Scientific Manuscript database

Biochar is a charcoal-like material produced by the thermochemical pyrolysis of biomass materials. It is being considered as a potentially significant means of storing carbon for long periods to mitigate greenhouse gases. Much of the interest comes from studies of Amazonian soils that appear to have...

STRUCTURES, INTRAMOLECULAR ROTATION BARRIERS, AND THERMOCHEMICAL PROPERTIES: ETHANOL, A-MONOETHANOLS, DICHLOROETHANOLS, AND CORRESPONDING RADICALS DERIVED FROM H ATOM LOSS. (R826371C009)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

Fate of higher-mass elements and surface functional groups during the pyrolysis of waste pecan shell

USDA-ARS?s Scientific Manuscript database

Thermochemical conversion of agricultural wastes to bioenergy has a potential to play forefront roles within the context of food, energy, and water nexus. Biochar solid product of pyrolysis is a promising tool to manage food crop production and water resources by means of soil amendment. The goal ...

Effects of hot-water extraction on the thermochemical conversion of shrub willow via fast pyrolysis

USDA-ARS?s Scientific Manuscript database

Hot-water extraction (TM) (HWE) is a pretreatment technology designed to facilitate the subsequent hydrolysis of cellulose by removing the majority of the hemicellulose and ash content from the solid biomass. The HWE process generates salable sugars and other products as part of the process. The bio...

Combination of biochar and poultry litter impact on soil properties and corn yield

USDA-ARS?s Scientific Manuscript database

Biochar, a by-product of a thermochemical process called pyrolysis, which involves burning of any agricultural and animal waste (biomass) under high temperature and absence of oxygen. It is assumed that since biochar is very high in aromatic carbon, which persists in soil environment for very long ...

Biochar as soil amendment to improve soil quality, crop yield, and carbon sequestration

USDA-ARS?s Scientific Manuscript database

Biochar, a by-product of a thermochemical process called pyrolysis, which involves burning of any agricultural and animal waste (biomass) under high temperature and absence of oxygen. It is assumed that since biochar is very high in aromatic carbon, which persists in soil environment for very long ...

Sheila Grady-McBride | NREL

Science.gov Websites

the Thermochemical Group. Prior to joining the National Renewable Energy Laboratory (NREL), Grady -McBride most recently worked at The Beck Group as a project assistant. Before that she worked for 12 years Beck Group, 2006-2012 Executive Assistant, VP of Quality, VP of Human Resources, Director of Training

Financial performance of a mobile pyrolysis system used to produce biochar from sawmill residues

Treesearch

Dongyeob Kim; Nathaniel McLean Anderson; Woodam Chung

2015-01-01

Primary wood products manufacturers generate significant amounts of woody biomass residues that can be used as feedstocks for distributed-scale thermochemical conversion systems that produce valuable bioenergy and bioproducts. However, private investment in these technologies is driven primarily by financial performance, which is often unknown for new technologies with...

THERMOCHEMICAL KINETIC ANALYSIS ON THE REACTIONS OF ALLYCIC ISOBUTENYL RADICAL WITH O2: AN ELEMENTARY REACTION MECHANISM FOR ISOBUTENE OXIDATION. (R824970)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

The Path of Carbon in Photosynthesis X. Carbon Dioxide Assimilation in Plants

DOE R&D Accomplishments Database

Calvin, M.; Bassham, J. A.; Benson, A. A.; Lynch, V.; Ouellet, C.; Schou, L.; Stepka, W.; Tolbert, N. E.

1950-04-01

The conclusions which have been drawn from the results of C{sup 14}O{sub 2} fixation experiments with a variety of plants are developed in this paper. The evidence for thermochemical reduction of carbon dioxide fixation intermediates is presented and the results are interpreted from such a viewpoint.

Remediation and recycling of WBP-treated lumber for use as flakeboard

Treesearch

Ronald Sabo; Jerrold E. Winandy; Carol A. Clausen; Altaf Basta

2008-01-01

Laboratory-scale experiments were conducted in which preservative metals (As, Cr, & Cu) were thermochemically extracted from CCA-treated spruce (Picea engelmannii) using oxalic acid and sodium hydroxide. The effects of extraction time, temperature, and pH were examined and laboratory scale optimization was achieved. Two series of experiments were carried out. In...

Estimating GHG Emissions from the Manufacturing of Field-Applied Biochar Pellets

Treesearch

Richard D. Bergman; Hanwen Zhang; Karl Englund; Keith Windell; Hongmei Gu

2016-01-01

Biochar application to forest soils can provide direct and indirect benefits, including carbon sequestration. Biochar, the result of thermochemical conversion of biomass, can have positive environmental climate benefits and can be more stable when field-applied to forest soils than wood itself. Categorizing greenhouse gas (GHG) emissions and carbon sequestration...

High-temperature Y267 EPDM elastomer: field and laboratory experiences, August 1981

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hirasuna, A.R.; Friese, G.J.; Stephens, C.A.

1982-03-01

Experiences which indicate the superiority of Y267 EPDM elastomer for high-temperature brines and other environments uses are summarized. Its good processing qualities, extremely good thermochemical stability, extremely good mechanical properties, its low-cost constituents, and its good performance in hydrocarbons are described in some case histories. (MCW)

Co-combustion of bituminous coal and biomass fuel blends: Thermochemical characterization, potential utilization and environmental advantage.

PubMed

Zhou, Chuncai; Liu, Guijian; Wang, Xudong; Qi, Cuicui

2016-10-01

The thermochemical characteristics and gaseous trace pollutant behaviors during co-combustion medium-to-low ash bituminous coal with typical biomass residues (corn stalk and sawdust) were investigated. Lowering of ignition index, burnout temperature and activation energy in the major combustion stage are observed in the coal/biomass blends. The blending proportion of 20% and 30% are regarded as the optimum blends for corn stalk and sawdust, respectively, in according the limitations of heating value, activation energy, flame stability and base/acid ratio. The reductions of gaseous As, Cd, Cu, Pb, Zn and polycyclic aromatic hydrocarbon (PAHs) were 4.5%, 7.8%, 6.3%, 9.8%, 9.4% and 17.4%, respectively, when co-combustion coal with 20% corn stalk. The elevated capture of trace elements were found in coal/corn stalk blend, while the coal/sawdust blend has the better PAHs control potential. The reduction mechanisms of gaseous trace pollutants were attributed to the fuel property, ash composition and relative residence time during combustion. Copyright © 2016 Elsevier Ltd. All rights reserved.

Green technology for conversion of renewable hydrocarbon based on plasma-catalytic approach

NASA Astrophysics Data System (ADS)

Fedirchyk, Igor; Nedybaliuk, Oleg; Chernyak, Valeriy; Demchina, Valentina

2016-09-01

The ability to convert renewable biomass into fuels and chemicals is one of the most important steps on our path to green technology and sustainable development. However, the complex composition of biomass poses a major problem for established conversion technologies. The high temperature of thermochemical biomass conversion often leads to the appearance of undesirable byproducts and waste. The catalytic conversion has reduced yield and feedstock range. Plasma-catalytic reforming technology opens a new path for biomass conversion by replacing feedstock-specific catalysts with free radicals generated in the plasma. We studied the plasma-catalytic conversion of several renewable hydrocarbons using the air plasma created by rotating gliding discharge. We found that plasma-catalytic hydrocarbon conversion can be conducted at significantly lower temperatures (500 K) than during the thermochemical ( 1000 K) and catalytic (800 K) conversion. By using gas chromatography, we determined conversion products and found that conversion efficiency of plasma-catalytic conversion reaches over 85%. We used obtained data to determine the energy yield of hydrogen in case of plasma-catalytic reforming of ethanol and compared it with other plasma-based hydrogen-generating systems.

Online residence time distribution measurement of thermochemical biomass pretreatment reactors

DOE PAGES

Sievers, David A.; Kuhn, Erik M.; Stickel, Jonathan J.; ...

2015-11-03

Residence time is a critical parameter that strongly affects the product profile and overall yield achieved from thermochemical pretreatment of lignocellulosic biomass during production of liquid transportation fuels. The residence time distribution (RTD) is one important measure of reactor performance and provides a metric to use when evaluating changes in reactor design and operating parameters. An inexpensive and rapid RTD measurement technique was developed to measure the residence time characteristics in biomass pretreatment reactors and similar equipment processing wet-granular slurries. Sodium chloride was pulsed into the feed entering a 600 kg/d pilot-scale reactor operated at various conditions, and aqueous saltmore » concentration was measured in the discharge using specially fabricated electrical conductivity instrumentation. This online conductivity method was superior in both measurement accuracy and resource requirements compared to offline analysis. Experimentally measured mean residence time values were longer than estimated by simple calculation and screw speed and throughput rate were investigated as contributing factors. In conclusion, a semi-empirical model was developed to predict the mean residence time as a function of operating parameters and enabled improved agreement.« less

Effects of thermochemical treatment on CuSbS 2 photovoltaic absorber quality and solar cell reproducibility

DOE PAGES

de Souza Lucas, Francisco Willian; Welch, Adam W.; Baranowski, Lauryn L.; ...

2016-08-01

CuSbS 2 is a promising nontoxic and earth-abundant photovoltaic absorber that is chemically simpler than the widely studied Cu 2ZnSnS 4. However, CuSbS 2 photovoltaic (PV) devices currently have relatively low efficiency and poor reproducibility, often due to suboptimal material quality and insufficient optoelectronic properties. To address these issues, here we develop a thermochemical treatment (TT) for CuSbS 2 thin films, which consists of annealing in Sb 2S 3 vapor followed by a selective KOH surface chemical etch. The annealed CuSbS 2 films show improved structural quality and optoelectronic properties, such as stronger band-edge photoluminescence and longer photoexcited carrier lifetime.more » These improvements also lead to more reproducible CuSbS 2 PV devices, with performance currently limited by a large cliff-type interface band offset with CdS contact. Altogether, these results point to the potential avenues to further increase the performance of CuSbS 2 thin film solar cell, and the findings can be transferred to other thin film photovoltaic technologies.« less

Proctor and gamble technology process assessment for bioenergy production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Hongqiang; Boardman, Richard Doin; Wright, Christopher Todd

P&G intends to replace as much as their current heat and power by renewable energy sources. For 2014, P&G’s total energy including electricity, natural gas and steam is approximately 1,540,000 MMBTU annually (Table 2). The biomass and wastes around P&G facility can be grouped into six categories (Figure 6): (1) Agriculture residue and grass, (2) Refuse (inorganic) solid material, (3) Food waste, (4) Organic waste stream, (5) livestock manure, (6) wastewater and sludge. The six feedstock sources can provide a total energy of 3,520,000 MMBTU per year (Table 10), among which the agriculture residue is the biggest fraction, about 67%,more » followed by livestock manures 27%. Therefore, the available energy sources around P&G facility are enough to meet their energy needs. These energy feedstocks would be treated by two processes: anaerobic digestion for biogas subsequently for heat and power and thermochemical process (combustion, pyrolysis and gasification) for heat and power (Figure 8 and 9). For AD, a one-stage complete mixing digester is preferable; and fluidized bed reactors are favorable for thermochemical process.« less

Thermochemical cyclic system for decomposing H/sub 2/O and/or CO/sub 2/ by means of cerium-titanium-sodium-oxygen compounds

DOEpatents

Bamberger, C.E.

1980-04-24

A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO/sub 2/), titanium dioxide (TiO/sub 2/) and sodium titanate (Na/sub 2/TiO/sub 3/) to form sodium cerous titanate (NaCeTi/sub 2/O/sub 6/) and oxygen. Sodium cerous titanate (NaCeTi/sub 2/O/sub 6/) reacted with sodium carbonate (Na/sub 2/CO/sub 3/) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle.

Thermochemical conversion of biomass in smouldering combustion across scales: The roles of heterogeneous kinetics, oxygen and transport phenomena.

PubMed

Huang, Xinyan; Rein, Guillermo

2016-05-01

The thermochemical conversion of biomass in smouldering combustion is investigated here by combining experiments and modeling at two scales: matter (1mg) and bench (100g) scales. Emphasis is put on the effect of oxygen (0-33vol.%) and oxidation reactions because these are poorly studied in the literature in comparison to pyrolysis. The results are obtained for peat as a representative biomass for which there is high-quality experimental data published previously. Three kinetic schemes are explored, including various steps of drying, pyrolysis and oxidation. The kinetic parameters are found using the Kissinger-Genetic Algorithm method, and then implemented in a one-dimensional model of heat and mass transfer. The predictions are validated with thermogravimetric and bench-scale experiments and then analyzed to unravel the role of heterogeneous reaction. This is the first time that the influence of oxygen on biomass smouldering is explained in terms of both chemistry and transport phenomena across scales. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

An MPI-CUDA approach for hypersonic flows with detailed state-to-state air kinetics using a GPU cluster

NASA Astrophysics Data System (ADS)

Bonelli, Francesco; Tuttafesta, Michele; Colonna, Gianpiero; Cutrone, Luigi; Pascazio, Giuseppe

2017-10-01

This paper describes the most advanced results obtained in the context of fluid dynamic simulations of high-enthalpy flows using detailed state-to-state air kinetics. Thermochemical non-equilibrium, typical of supersonic and hypersonic flows, was modeled by using both the accurate state-to-state approach and the multi-temperature model proposed by Park. The accuracy of the two thermochemical non-equilibrium models was assessed by comparing the results with experimental findings, showing better predictions provided by the state-to-state approach. To overcome the huge computational cost of the state-to-state model, a multiple-nodes GPU implementation, based on an MPI-CUDA approach, was employed and a comprehensive code performance analysis is presented. Both the pure MPI-CPU and the MPI-CUDA implementations exhibit excellent scalability performance. GPUs outperform CPUs computing especially when the state-to-state approach is employed, showing speed-ups, of the single GPU with respect to the single-core CPU, larger than 100 in both the case of one MPI process and multiple MPI process.

Design and cost analysis for an ammonia-based solar thermochemical cavity absorber

NASA Astrophysics Data System (ADS)

Williams, O. M.

1980-01-01

A design and cost analysis is introduced for a solar thermochemical cavity absorber operated at the focus of a tracking paraboloidal concentrator and based on the ammonia dissociation reaction. The absorber design consists of a catalyst-filled nickel alloy tube wound into a spiral forming the inner cavity wall and shaped to match the incident power density profile to the reactor heat requirements. The reactor tube is welded to a coaxial counterflow heat exchanger. The relationships among the power density profile, the reaction thermodynamics and kinetics, and the heat transfer characteristics are examined in detail and it is shown that an installed cost goal of typically 10 U.S. dollars per square meter of solar collector area can be achieved through use of high activity ammonia dissociation catalyst. The optimum absorber size for a given paraboloidal dish area is calculated for a system pressure of 20 MPa and it is shown that a cost effective absorber suitable for 100,000-hr operation would operate at 90% efficiency at 750 C wall temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, K. C., Adams; Thomas, T; Eiteman, Mark A

In this project we focused on several aspects of technology development that advances the formation of an integrated biorefinery. These focus areas include: [ 1] pretreatment of biomass to enhance quality of products from thermochemical conversion; [2] characterization of and development of coproduct uses; [3] advancement in fermentation of lignocellulosics and particularly C5 and C6 sugars simultaneously, and [ 4] development of algal biomass as a potential substrate for the biorefinery. These advancements are intended to provide a diverse set of product choices within the biorefinery, thus improving the cost effectiveness of the system. Technical effectiveness was demonstrated in themore » thermochemical product quality in the form of lower tar production, simultaneous of use of multiple sugars in fermentation, use ofbiochar in environmental (ammonia adsorption) and agricultural applications, and production of algal biomass in wastewaters. Economic feasibility of algal biomass production systems seems attractive, relative to the other options. However, further optimization in all paths, and testing/demonstration at larger scales are required to fully understand the economic viabilities. The coproducts provide a clear picture that multiple streams of value can be generated within an integrated biorefinery, and these include fuels and products.« less

Mild-temperature thermochemical pretreatment of green macroalgal biomass: Effects on solubilization, methanation, and microbial community structure.

PubMed

Jung, Heejung; Baek, Gahyun; Kim, Jaai; Shin, Seung Gu; Lee, Changsoo

2016-01-01

The effects of mild-temperature thermochemical pretreatments with HCl or NaOH on the solubilization and biomethanation of Ulva biomass were assessed. Within the explored region (0-0.2M HCl/NaOH, 60-90°C), both methods were effective for solubilization (about 2-fold increase in the proportion of soluble organics), particularly under high-temperature and high-chemical-dose conditions. However, increased solubilization was not translated into enhanced biogas production for both methods. Response surface analysis statistically revealed that HCl or NaOH addition enhances the solubilization degree while adversely affects the methanation. The thermal-only treatment at the upper-limit temperature (90°C) was estimated to maximize the biogas production for both methods, suggesting limited potential of HCl/NaOH treatment for enhanced Ulva biomethanation. Compared to HCl, NaOH had much stronger positive and negative effects on the solubilization and methanation, respectively. Methanosaeta was likely the dominant methanogen group in all trials. Bacterial community structure varied among the trials according primarily to HCl/NaOH addition. Copyright © 2015 Elsevier Ltd. All rights reserved.

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor

PubMed Central

2016-01-01

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H2O and CO2. The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kWth lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O2 for smaller particles. PMID:27853339

Positronium hydride in hydrogen-laden thermochemically reduced MgO single crystals

NASA Astrophysics Data System (ADS)

Pareja, R.; de La Cruz, R. M.; Pedrosa, M. A.; González, R.; Chen, Y.

1990-04-01

Thermochemical reduction of hydrogen-laden MgO single crystals at T~2400 K results in a large concentration of both hydride (H-) ions and anion vacancies (>1024 m-3). Positron-lifetime experiments of these crystals provide evidence for bound positronium hydride states also referred to as [e+-H-] or PsH states. The presence of the anion vacancies was found to inhibit the formation of these states. After thermally annealing out these vacancies, such that H- concentration remains intact, two long-lived components appear in the lifetime spectrum. Furthermore, these two components correlate with the presence of the H-ions. These results suggest the existence of bound [e+-H-] states when positrons are trapped by the H- ions, and the subsequent formation of positronium (Ps) states by the dissociation of the [e+-H-] states. From the values of the intermediate lifetime component, a value of (570+/-50) ps is obtained for the lifetime of the PsH state located in an anion vacancy in MgO. The longest lifetime component ~(1-3) ns is attributed to pick-off annihilation of ortho-Ps states.

Life cycle assessment of hydrogen production from S-I thermochemical process coupled to a high temperature gas reactor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Giraldi, M. R.; Francois, J. L.; Castro-Uriegas, D.

The purpose of this paper is to quantify the greenhouse gas (GHG) emissions associated to the hydrogen produced by the sulfur-iodine thermochemical process, coupled to a high temperature nuclear reactor, and to compare the results with other life cycle analysis (LCA) studies on hydrogen production technologies, both conventional and emerging. The LCA tool was used to quantify the impacts associated with climate change. The product system was defined by the following steps: (i) extraction and manufacturing of raw materials (upstream flows), (U) external energy supplied to the system, (iii) nuclear power plant, and (iv) hydrogen production plant. Particular attention wasmore » focused to those processes where there was limited information from literature about inventory data, as the TRISO fuel manufacture, and the production of iodine. The results show that the electric power, supplied to the hydrogen plant, is a sensitive parameter for GHG emissions. When the nuclear power plant supplied the electrical power, low GHG emissions were obtained. These results improve those reported by conventional hydrogen production methods, such as steam reforming. (authors)« less

State-of-the-art thermochemical and kinetic computations for astrochemical complex organic molecules: formamide formation in cold interstellar clouds as a case study

PubMed Central

Vazart, Fanny; Calderini, Danilo; Puzzarini, Cristina; Skouteris, Dimitrios

2017-01-01

We propose an integrated computational strategy aimed at providing reliable thermochemical and kinetic information on the formation processes of astrochemical complex organic molecules. The approach involves state-of-the-art quantum-mechanical computations, second-order vibrational perturbation theory, and kinetic models based on capture and transition state theory together with the master equation approach. Notably, tunneling, quantum reflection, and leading anharmonic contributions are accounted for in our model. Formamide has been selected as a case study in view of its interest as a precursor in the abiotic amino acid synthesis. After validation of the level of theory chosen for describing the potential energy surface, we have investigated several pathways of the OH+CH2NH and NH2+HCHO reaction channels. Our results indicate that both reaction channels are essentially barrier-less (in the sense that all relevant transition states lie below or only marginally above the reactants) and can, therefore, occur under the low temperature conditions of interstellar objects provided that tunneling is taken into the proper account. PMID:27689448

Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

PubMed

Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

2015-06-08

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental Demonstration of the Thermochemical Reduction of Ceria in a Solar Aerosol Reactor.

PubMed

Welte, Michael; Barhoumi, Rafik; Zbinden, Adrian; Scheffe, Jonathan R; Steinfeld, Aldo

2016-10-12

We report on the experimental demonstration of an aerosol solar reactor for the thermal reduction of ceria, as part of a thermochemical redox cycle for splitting H 2 O and CO 2 . The concept utilizes a cavity-receiver enclosing an array of alumina tubes, each containing a downward gravity-driven aerosol flow of ceria particles countercurrent to an inert sweep gas flow for intrinsic separation of reduced ceria and oxygen. A 2 kW th lab-scale prototype with a single tube was tested under radiative fluxes approaching 4000 suns, yielding reaction extents of up to 53% of the thermodynamic equilibrium at 1919 K within residence times below 1 s. Upon thermal redox cycling, fresh primary particles of 2.44 μm mean size initially formed large agglomerates of 1000 μm mean size, then sintered into stable particles of 150 μm mean size. The reaction extent was primarily limited by heat transfer for large particles/agglomerates (mean size > 200 μm) and by the gas phase advection of product O 2 for smaller particles.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Zhiwen

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 willmore » 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.« less

Identification and thermochemical analysis of high-lignin feedstocks for biofuel and biochemical production

PubMed Central

2011-01-01

Background Lignin is a highly abundant biopolymer synthesized by plants as a complex component of plant secondary cell walls. Efforts to utilize lignin-based bioproducts are needed. Results Herein we identify and characterize the composition and pyrolytic deconstruction characteristics of high-lignin feedstocks. Feedstocks displaying the highest levels of lignin were identified as drupe endocarp biomass arising as agricultural waste from horticultural crops. By performing pyrolysis coupled to gas chromatography-mass spectrometry, we characterized lignin-derived deconstruction products from endocarp biomass and compared these with switchgrass. By comparing individual pyrolytic products, we document higher amounts of acetic acid, 1-hydroxy-2-propanone, acetone and furfural in switchgrass compared to endocarp tissue, which is consistent with high holocellulose relative to lignin. By contrast, greater yields of lignin-based pyrolytic products such as phenol, 2-methoxyphenol, 2-methylphenol, 2-methoxy-4-methylphenol and 4-ethyl-2-methoxyphenol arising from drupe endocarp tissue are documented. Conclusions Differences in product yield, thermal decomposition rates and molecular species distribution among the feedstocks illustrate the potential of high-lignin endocarp feedstocks to generate valuable chemicals by thermochemical deconstruction. PMID:22018114

Overview of current biological and thermo-chemical treatment technologies for sustainable sludge management.

PubMed

Zhang, Linghong; Xu, Chunbao Charles; Champagne, Pascale; Mabee, Warren

2014-07-01

Sludge is a semi-solid residue produced from wastewater treatment processes. It contains biodegradable and recalcitrant organic compounds, as well as pathogens, heavy metals, and other inorganic constituents. Sludge can also be considered a source of nutrients and energy, which could be recovered using economically viable approaches. In the present paper, several commonly used sludge treatment processes including land application, composting, landfilling, anaerobic digestion, and combustion are reviewed, along with their potentials for energy and product recovery. In addition, some innovative thermo-chemical techniques in pyrolysis, gasification, liquefaction, and wet oxidation are briefly introduced. Finally, a brief summary of selected published works on the life cycle assessment of a variety of sludge treatment and end-use scenarios is presented in order to better understand the overall energy balance and environmental burdens associated with each sludge treatment pathway. In all scenarios investigated, the reuse of bioenergy and by-products has been shown to be of crucial importance in enhancing the overall energy efficiency and reducing the carbon footprint. © The Author(s) 2014.

Thermochemical cyclic system for decomposing H.sub.2 O and/or CO.sub.2 by means of cerium-titanium-sodium-oxygen compounds

DOEpatents

Bamberger, Carlos E.

1982-01-01

A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO.sub.2), titanium dioxide (TiO.sub.2) and sodium titanate (Na.sub.2 TiO.sub.3) to form sodium cerous titanate (NaCeTi.sub.2 O.sub.6) and oxygen. Sodium cerous titanate (NaCeTi.sub.2 O.sub.6) reacted with sodium carbonate (Na.sub.2 CO.sub.3) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle.

Marsilea spp.-A novel source of lignocellulosic biomass: Effect of solubilized lignin on anaerobic biodegradability and cost of energy products.

PubMed

Rajesh Banu, J; Sugitha, S; Kannah, R Yukesh; Kavitha, S; Yeom, Ick Tae

2018-05-01

The present study concerns the liquefying potential of an unusual source of lignocellulosic biomass (Marsilea spp., water clover, an aquatic fern) during combinative pretreatment. The focus was on how the pretreatment affects the biodegradability, methane production, and profitability of thermochemical dispersion disintegration (TCDD) based on liquefaction and soluble lignin. The TCDD process was effective at 12,000 rpm and 11 min under the optimized thermochemical conditions (80 °C and pH 11). The results from biodegradability tests imply that 30% liquefaction was sufficient to achieve enhanced biodegradability of about 0.280 g-COD/g-COD. When biodegradability was >30% inhibition was observed (0.267 and 0.264 g-COD/g-COD at 35-40% liquefaction) due to higher soluble lignin release (4.53-4.95 g/L). Scalable studies revealed that achievement of 30% liquefaction was beneficial in terms of the energy and cost benefit ratios (0.956 and 1.02), when compared to other choices. Copyright © 2018 Elsevier Ltd. All rights reserved.

The Thermochemical and Kinetic Properties of Ascorbate are Tuned by its Local Environment: Solution Chemistry and Biochemical Implications

PubMed Central

Warren, Jeffrey J.; Mayer, James M.

2010-01-01

Ascorbate (Vitamin C) is a ubiquitous biological cofactor. While its aqueous solution chemistry has long been studied, many in vivo reactions of ascorbate occur in enzyme active sites or at membrane interfaces, which have varying local environments. This report shows that the rate and driving force of oxidations of two ascorbate derivatives by the TEMPO radical (2,2′-6,6′-tetramethylpiperidine-1-oxyl) in acetonitrile are very sensitive to the presence of various additives. These reactions proceed by the transfer of a proton and an electron (a hydrogen atom), as is typical of biological ascorbate reactions. The measured rate and equilibrium constants vary substantially with added water or other polar solutes in acetonitrile solutions, indicating large shifts in the reducing power of ascorbate. The correlation of rate and equilibrium constants indicates that this effect has a thermochemical origin rather than being a purely kinetic effect. This contrasts with previous examples of solvent effects on hydrogen atom transfer reactions. Potential biological implications of this apparently unique effect are discussed. PMID:20476757

Stochastic effects in a thermochemical system with Newtonian heat exchange.

PubMed

Nowakowski, B; Lemarchand, A

2001-12-01

We develop a mesoscopic description of stochastic effects in the Newtonian heat exchange between a diluted gas system and a thermostat. We explicitly study the homogeneous Semenov model involving a thermochemical reaction and neglecting consumption of reactants. The master equation includes a transition rate for the thermal transfer process, which is derived on the basis of the statistics for inelastic collisions between gas particles and walls of the thermostat. The main assumption is that the perturbation of the Maxwellian particle velocity distribution can be neglected. The transition function for the thermal process admits a continuous spectrum of temperature changes, and consequently, the master equation has a complicated integro-differential form. We perform Monte Carlo simulations based on this equation to study the stochastic effects in the Semenov system in the explosive regime. The dispersion of ignition times is calculated as a function of system size. For sufficiently small systems, the probability distribution of temperature displays transient bimodality during the ignition period. The results of the stochastic description are successfully compared with those of direct simulations of microscopic particle dynamics.

A pyrolysis study for the thermal and kinetic characteristics of an agricultural waste with two different plastic wastes.

PubMed

Çepelioğullar, Özge; Pütün, Ayşe E

2014-10-01

In this study, thermochemical conversion of plastic wastes (PET and PVC) together with an agricultural waste (hazelnut shell) was investigated. In order to determine the thermal and kinetic behaviours, pyrolysis experiments were carried out from room temperature to 800 °C, with a heating rate of 10 °C min(-1) in the presence of a N2 atmosphere in a thermogravimetric analyzer. With the obtained thermogravimetric data, an appropriate temperature was specified for the pyrolysis of biomass-plastic wastes in a fixed-bed reactor. At the second step, pyrolysis experiments were carried out at the same conditions with the thermogravimetric analyzer, except the final temperature which was up to 500 °C in this case. After pyrolysis experiments, pyrolysis yields were calculated and characterization studies for bio-oil were investigated. Experimental results showed that co-pyrolysis has an important role in the determination of the pyrolysis mechanism and the process conditions while designing/implementing a thermochemical conversion method where biomass-plastic materials were preferred as raw materials. © The Author(s) 2014.

Techno-economic comparison of biojet fuel production from lignocellulose, vegetable oil and sugar cane juice.

PubMed

Diederichs, Gabriel Wilhelm; Ali Mandegari, Mohsen; Farzad, Somayeh; Görgens, Johann F

2016-09-01

In this study, a techno-economic comparison was performed considering three processes (thermochemical, biochemical and hybrid) for production of jet fuel from lignocellulosic biomass (2G) versus two processes from first generation (1G) feedstocks, including vegetable oil and sugar cane juice. Mass and energy balances were constructed for energy self-sufficient versions of these processes, not utilising any fossil energy sources, using ASPEN Plus® simulations. All of the investigated processes obtained base minimum jet selling prices (MJSP) that is substantially higher than the market jet fuel price (2-4 fold). The 1G process which converts vegetable oil, obtained the lowest MJSPs of $2.22/kg jet fuel while the two most promising 2G processes- the thermochemical (gasification and Fischer-Tropsch synthesis) and hybrid (gasification and biochemical upgrading) processes- reached MJSPs of $2.44/kg and $2.50/kg jet fuel, respectively. According to the economic sensitivity analysis, the feedstock cost and fixed capital investment have the most influence on the MJSP. Copyright © 2016 Elsevier Ltd. All rights reserved.

Research and evaluation of biomass resources/conversion/utilization systems (market/experimental analysis for development of a data base for a fuels from biomass model. Volume I. Biomass allocation model. Technical progress report for the period ending September 30, 1980

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Y.K.; Chen, H.T.; Helm, R.W.

1980-01-01

A biomass allocation model has been developed to show the most profitable combination of biomass feedstocks thermochemical conversion processes, and fuel products to serve the seasonal conditions in a regional market. This optimization model provides a tool for quickly calculating the most profitable biomass missions from a large number of potential biomass missions. Other components of the system serve as a convenient storage and retrieval mechanism for biomass marketing and thermochemical conversion processing data. The system can be accessed through the use of a computer terminal, or it could be adapted to a portable micro-processor. A User's Manual for themore » system has been included in Appendix A of the report. The validity of any biomass allocation solution provided by the allocation model is dependent on the accuracy of the data base. The initial data base was constructed from values obtained from the literature, and, consequently, as more current thermochemical conversion processing and manufacturing costs and efficiencies become available, the data base should be revised. Biomass derived fuels included in the data base are the following: medium Btu gas low Btu gas, substitute natural gas, ammonia, methanol, electricity, gasoline, and fuel oil. The market sectors served by the fuels include: residential, electric utility, chemical (industrial), and transportation. Regional/seasonal costs and availabilities and heating values for 61 woody and non-woody biomass species are included. The study has included four regions in the United States which were selected because there was both an availability of biomass and a commercial demand for the derived fuels: Region I: NY, WV, PA; Region II: GA, AL, MS; Region III: IN, IL, IA; and Region IV: OR, WA.« less

Hyperthermophile Protein Behavior: Partially-Structured Conformations of Pyrococcus furiosus Rubredoxin Monomers Generated through Forced Cold-Denaturation and Refolding

PubMed Central

Ahmed, Shubbir; Guptasarma, Purnananda

2014-01-01

Some years ago, we showed that thermo-chemically denatured, partially-unfolded forms of Pyrococcus furiosus triosephosphateisomerase (PfuTIM) display cold-denaturation upon cooling, and heat-renaturation upon reheating, in proportion with the extent of initial partial unfolding achieved. This was the first time that cold-denaturation was demonstrated for a hyperthermophile protein, following unlocking of surface salt bridges. Here, we describe the behavior of another hyperthermophile protein, the small, monomeric, 53 residues-long rubredoxin from Pyrococcus furiosus (PfRd), which is one of the most thermostable proteins known to man. Like PfuTIM, PfRd too displays cold-denaturation after initial thermo-chemical perturbation, however, with two differences: (i) PfRd requires considerably higher temperatures as well as higher concentrations of guanidium hydrochloride (Gdm.HCl) than PfuTIM; (ii) PfRd's cold-denaturation behavior during cooling after thermo-chemical perturbation is incompletely reversible, unlike PfuTIM's, which was clearly reversible (from each different conformation generated). Differential cold-denaturation treatments allow PfRd to access multiple partially-unfolded states, each of which is clearly highly kinetically-stable. We refer to these as ‘Trishanku’ unfolding intermediates (or TUIs). Fascinatingly, refolding of TUIs through removal of Gdm.HCl generates multiple partially-refolded, monomeric, kinetically-trapped, non-native ‘Trishanku’ refolding intermediates (or TRIs), which differ from each other and from native PfRd and TUIs, in structural content and susceptibility to proteolysis. We find that the occurrence of cold denaturation and observations of TUI and TRI states is contingent on the oxidation status of iron, with redox agents managing to modulate the molecule's behavior upon gaining access to PfRd's iron atom. Mass spectrometric examination provides no evidence of the formation of disulfide bonds, but other experiments suggest that the oxidation status of iron (and its extent of burial) together determine whether or not PfRd shows cold denaturation, and also whether redox agents are able to modulate its behavior. PMID:24603413

Assessing thermochemical data

NASA Astrophysics Data System (ADS)

Holmes, John L.; Aubry, Christiane; Wang, Xian

2007-11-01

This paper describes, with examples, a critical assessment of thermochemical data for some small molecules and free radicals. The available heats of formation, [Delta]fH° (all 298 K values). for simple alkyl hydroperoxides and di-alkyl peroxides were compared and new data are provided. The [Delta]fH° values, all ±5 kJ/mol, are: CH3OOH, -135; CH3CH2OOH, -168; n-C3H7OOH, -189; s-C3H7OOH, -205; t-C4H9OOH, -240; CH3OOCH3, -132; CH3CH2OOCH3, -165; C2H5OOC2H5, -198; n-C3H7OOn-C3H7, -240; s-C3H7OOs-C3H7, -272; t-C4H9OOt-C4H9, -342. These are consistent with established O-O bond dissociation energies and with additivity considerations. [Delta]fH° values for the corresponding alkoxy radicals are also addressed. A similar survey was applied to the homologous n-alkyl aldehydes, C2 to C8, for which recommended [Delta]fH° values, all ±1.5 kJ/mol, are: -166.5, -189, -207.5, -227, -248, -268 and -289, respectively. Particular attention was given to [Delta]fH°(CH3CO) = -10.3 ± 1.8 kJ/mol. The current NIST WebBook datum, [Delta]fH°(CS) = 280.3 kJ/mol, is arguably the best value, being consistent with related thermochemical data. Finally the [Delta]fH° values for the allylic free radicals CH2CHCH2, 174 ± 3 kJ/mol, CH2CHCH(OH), 4.5 ± 4 kJ/mol, and (CH2CH)2C(OH), 37 ± 4 kJ/mol, derived from experimental data and results of computational chemistry are described, together with some related homolytic bond strengths.

ThermoFit: A Set of Software Tools, Protocols and Schema for the Organization of Thermodynamic Data and for the Development, Maintenance, and Distribution of Internally Consistent Thermodynamic Data/Model Collections

NASA Astrophysics Data System (ADS)

Ghiorso, M. S.

2013-12-01

Internally consistent thermodynamic databases are critical resources that facilitate the calculation of heterogeneous phase equilibria and thereby support geochemical, petrological, and geodynamical modeling. These 'databases' are actually derived data/model systems that depend on a diverse suite of physical property measurements, calorimetric data, and experimental phase equilibrium brackets. In addition, such databases are calibrated with the adoption of various models for extrapolation of heat capacities and volumetric equations of state to elevated temperature and pressure conditions. Finally, these databases require specification of thermochemical models for the mixing properties of solid, liquid, and fluid solutions, which are often rooted in physical theory and, in turn, depend on additional experimental observations. The process of 'calibrating' a thermochemical database involves considerable effort and an extensive computational infrastructure. Because of these complexities, the community tends to rely on a small number of thermochemical databases, generated by a few researchers; these databases often have limited longevity and are universally difficult to maintain. ThermoFit is a software framework and user interface whose aim is to provide a modeling environment that facilitates creation, maintenance and distribution of thermodynamic data/model collections. Underlying ThermoFit are data archives of fundamental physical property, calorimetric, crystallographic, and phase equilibrium constraints that provide the essential experimental information from which thermodynamic databases are traditionally calibrated. ThermoFit standardizes schema for accessing these data archives and provides web services for data mining these collections. Beyond simple data management and interoperability, ThermoFit provides a collection of visualization and software modeling tools that streamline the model/database generation process. Most notably, ThermoFit facilitates the rapid visualization of predicted model outcomes and permits the user to modify these outcomes using tactile- or mouse-based GUI interaction, permitting real-time updates that reflect users choices, preferences, and priorities involving derived model results. This ability permits some resolution of the problem of correlated model parameters in the common situation where thermodynamic models must be calibrated from inadequate data resources. The ability also allows modeling constraints to be imposed using natural data and observations (i.e. petrologic or geochemical intuition). Once formulated, ThermoFit facilitates deployment of data/model collections by automated creation of web services. Users consume these services via web-, excel-, or desktop-clients. ThermoFit is currently under active development and not yet generally available; a limited capability prototype system has been coded for Macintosh computers and utilized to construct thermochemical models for H2O-CO2 mixed fluid saturation in silicate liquids. The longer term goal is to release ThermoFit as a web portal application client with server-based cloud computations supporting the modeling environment.

Comprehensive Assessment of Composition and Thermochemical Variability by High Resolution GC/QToF-MS and the Advanced Distillation-Curve Method as a Basis of Comparison for Reference Fuel Development*

PubMed Central

Lovestead, Tara M.; Burger, Jessica L.; Schneider, Nico; Bruno, Thomas J.

2018-01-01

Commercial and military aviation is faced with challenges that include high fuel costs, undesirable emissions, and supply chain insecurity that result from the reliance on petroleum-based feedstocks. The development of alternative gas turbine fuels from renewable resources will likely be part of addressing these issues. The United States has established a target for one billion gallons of renewable fuels to enter the supply chain by 2018. These alternative fuels will have to be very similar in properties, chemistry, and composition to existing fuels. To further this goal, the National Jet Fuel Combustion Program (a collaboration of multiple U.S. agencies under the auspices of the Federal Aviation Administration, FAA) is coordinating measurements on three reference gas turbine fuels to be used as a basis of comparison. These fuels are reference fuels with certain properties that are at the limits of experience. These fuels include a low viscosity, low flash point, high hydrogen content “best case” JP-8 (POSF 10264) fuel, a relatively high viscosity, high flash point, low hydrogen content “worst case” JP-5 (POSF 10259) fuel, and a Jet-A (POSF 10325) fuel with relatively average properties. A comprehensive speciation of these fuels is provided in this paper by use of high resolution gas chromatography/quadrupole time-of-flight – mass spectrometry (GC/QToF-MS), which affords unprecedented resolution and exact molecular formula capabilities. The volatility information as derived from the measurement of the advanced distillation curve temperatures, Tk and Th, provides an approximation of the vapor liquid equilibrium and examination of the composition channels provides detailed insight into thermochemical data. A comprehensive understanding of the compositional and thermophysical data of gas turbine fuels is required not only for comparison but also for modeling of such complex mixtures, which will, in turn, aid in the development of new fuels with the goals of diversified feedstocks, decreased pollution, and increased efficiency. PMID:29706688

Thermodynamics and performance of the Mg-H-F system for thermochemical energy storage applications.

PubMed

Tortoza, Mariana S; Humphries, Terry D; Sheppard, Drew A; Paskevicius, Mark; Rowles, Matthew R; Sofianos, M Veronica; Aguey-Zinsou, Kondo-Francois; Buckley, Craig E

2018-01-24

Magnesium hydride (MgH 2 ) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH 2 to form a range of Mg(H x F 1-x ) 2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H 0.85 F 0.15 ) 2 having a maximum rate of H 2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H 2 (theoretical 5.4 wt% H 2 ). An extremely stable Mg(H 0.43 F 0.57 ) 2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H 2 is not released until above 505 °C. PCI measurements of Mg(H 0.85 F 0.15 ) 2 have determined the enthalpy (ΔH des ) to be 73.6 ± 0.2 kJ mol -1 H 2 and entropy (ΔS des ) to be 131.2 ± 0.2 J K -1 mol -1 H 2 , which is slightly lower than MgH 2 with ΔH des of 74.06 kJ mol -1 H 2 and ΔS des = 133.4 J K -1 mol -1 H 2 . Cycling studies of Mg(H 0.85 F 0.15 ) 2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ∼80 °C compared to bulk MgH 2 , increasing the thermal operating temperatures for technological applications.

Thermochemical Process Integration, Scale-Up, and Piloting Publications |

Science.gov Websites

-Economic Assessment of Ex Situ Catalytic Fast Pyrolysis of Biomass: A Fixed Bed Reactor Implementation Scenario for Future Feasibility, Topics in Catalysis Image of a schematic of hot gas filter and ex situ Research Pathways with In Situ and Ex Situ Upgrading of Fast Pyrolysis Vapors, NREL Technical Report Image

Method for Biochar Passivation Using Low Percent Oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Kristin; Dupuis, Dan; Wilcox, Esther

2016-06-06

The thermochemical process development unit may be configured for pyrolysis or gasification. The pyrolysis unit operations include: feed transport system; entrained flow reactor; solids removal and collection; and liquid scrubbing, collection, and filtration. Char accumulates in the collection drums at a rate of ~1.5 kg/hr and must be passivated before it is stored or transported.

Physical Vapor Transport of Lead Telluride

NASA Technical Reports Server (NTRS)

Palosz, W.

1997-01-01

Mass transport properties of physical vapor transport of PbTe are investigated. Thermochemical analysis of the system and its implications for the growth conditions are discussed. The effect of the material preparation and pre-processing on the stoichiometry and residual gas pressure and composition, and on related mass flux is shown. A procedure leading to high mass transport rates is presented.

Potential heat exchange fluids for use in sulfuric acid vaporizers

NASA Technical Reports Server (NTRS)

Lawson, D. D.; Petersen, G. R.

1979-01-01

A series of perhalocarbons are proposed as candidate heat exchange fluids for service in thermochemical cycles for hydrogen production that involve direct contact of the fluid with sulfuric acid and vaporization of the acid. The required chemical and physical criteria of the liquids are described and the results of some preliminary high temperature test data are presented.

A Herschel survey of outbursting sources .

NASA Astrophysics Data System (ADS)

Postel, A.; Audard, M.; Vorobyov, E.; Rab, C.; Dionatos, O.; Güdel, M.

We present the current progress of our investigation of 12 FU Orionis (FUors) and EXor (from the prototype, EX Lup) objects. The observational spectroscopic and photometric data of mainly Herschel and Spitzer will be accompanied by hydrodynamical simulations and thermo-chemical modeling in a Swiss-Austrian collaboration, aiming to improve our understanding of episodic outbursts of low-mass young stars.

Silver(II) Oxide or Silver(I,III) Oxide?

ERIC Educational Resources Information Center

Tudela, David

2008-01-01

The often called silver peroxide and silver(II) oxide, AgO or Ag[subscript 2]O[subscript 2], is actually a mixed oxidation state silver(I,III) oxide. A thermochemical cycle, with lattice energies calculated within the "volume-based" thermodynamic approach, explain why the silver(I,III) oxide is more stable than the hypothetical silver(II) oxide.…

Production of nitrogen oxides in air pulse-periodic discharge with apokamp

NASA Astrophysics Data System (ADS)

Panarin, Victor A.; Skakun, Victor S.; Sosnin, Eduard A.; Tarasenko, Victor F.

2018-05-01

The decomposition products of pulse-periodic discharge atmospheric pressure plasma in apokamp, diffuse and corona modes were determined by optical and chemical methods. It is shown that apokamp discharge formation starts at a critical value of dissipation power in a discharge channel. Simultaneously, due to the thermochemical reactions, plasma starts to efficiently produce nitrogen oxides.

Difference rule-a new thermodynamic principle: prediction of standard thermodynamic data for inorganic solvates.

PubMed

Jenkins, H Donald Brooke; Glasser, Leslie

2004-12-08

We present a quite general thermodynamic "difference" rule, derived from thermochemical first principles, quantifying the difference between the standard thermodynamic properties, P, of a solid n-solvate (or n-hydrate), n-S, containing n molecules of solvate, S (water or other) and the corresponding solid parent (unsolvated) salt: [P[n-solvate] - P[parent

Impact of harvest time and switchgrass cultivar on conversion to sugars and pyrolysis oils using biochemical and thermochemical routes

USDA-ARS?s Scientific Manuscript database

Switchgrass (Panicum virgatum L.), a perennial grass native to much of North America, is undergoing development as a dedicated energy crop. While high-biomass yield is necessary for the development of switchgrass as a bioenergy crop, composition of the biomass and nutrient content as they relate to...

Thermochemical Process Integration, Scale-Up, and Piloting | Bioenergy |

Science.gov Websites

; represented by spheres of hydrogen and carbon monoxide, then to "Gas Cleanup, Solids Removal, Reforming ; represented by a gasoline dispenser nozzle. A green arrow of "Fast Pyrolysis" and blue arrows for Distillation," and finally to "Fuels," represented by a gasoline dispenser nozzle Variety of

Comparative sorption and leaching study of the herbicides fluometuron and MCPA in a soil amended with biochar and other sorbents

USDA-ARS?s Scientific Manuscript database

Biochar is the solid residual remaining after the thermo-chemical transformation of biomass and, because of its numerous properties; it has been proposed to be used as soil amendment. In this work, the effect of soil amendment with six biochars from different feedstocks, production, and post-product...

NREL's Thermochemical Conversion Facility Video Text Version | Bioenergy |

Science.gov Websites

steady-state. We use a tandem fast pyrolysis reactor and Davison recirculating reactor system to study ex be continually added and withdrawn so we can study catalyst activity and product composition at catalyst. Here we can study the impact of catalyst formulation and processing conditions on bio-oil

Ceramic Integration Technologies for Energy and Aerospace Applications

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay; Asthana, Ralph N.

2007-01-01

Robust and affordable integration technologies for advanced ceramics are required to improve the performance, reliability, efficiency, and durability of components, devices, and systems based on them in a wide variety of energy, aerospace, and environmental applications. Many thermochemical and thermomechanical factors including joint design, analysis, and optimization must be considered in integration of similar and dissimilar material systems.

Examination of Mechanisms and Fuel-Molecular Effects on Soot Formation.

DTIC Science & Technology

1986-12-10

Naegeli , D.W., Dryer, F.L., and Glassman, I., Env. Sci. Tech. 8, 43 (1974). 6. Kee, R.J., Miller, J.A., Jefferson, T.H.: "CHEMKIN: A General-Purpose...Springer Verlag, New York, 1984. 16. Benson, S.W.: Thermochemical Kinetics, J. Wiley and Sons, New York (1976). 15 % 17. Colket, M.B., Naegeli , D.W., and

Greenhouse gas emission and groundwater pollution potentials of soils amended with raw and carbonized swine solids

USDA-ARS?s Scientific Manuscript database

The objective of this research is to study the greenhouse gas emission and groundwater pollution potentials of the soils amended with raw swine solids and swine biochars made from different thermochemical conditions. Triplicate sets of small pots were designed: 1) control soil with a 50/50 mixture o...

Studies on Ammonia Spectral Signatures Relevant to Jupiter's Clouds

NASA Astrophysics Data System (ADS)

Kalogerakis, Konstantinos S.; Oza, A. U.; Marschall, J.; Wong, M. H.

2006-09-01

Observational evidence and thermochemical models indicate an abundance of ammonia ice clouds in Jupiter's atmosphere. However, spectrally identifiable ammonia ice clouds are found covering less than 1% of Jupiter's atmosphere, notably in turbulent areas [1,2]. Current literature suggests two possible explanations: coating by a hydrocarbon haze and/or photochemical processing ("tanning") [2,3]. We are pursuing a research program investigating the above hypotheses. In the experiments, thin films of ammonia ices are deposited in a cryogenic apparatus, coated with hydrocarbons, and characterized by infrared spectroscopy. The ice films can be irradiated by ultraviolet light to study their photochemistry. The spectroscopic measurements aim to identify the processes that control the optical properties of the ice mixtures and quantify their dependence on the identity of the coating, the temperature, and the ice composition. We have observed a consistent suppression of the ammonia absorption feature at 3 μm with coverage by thin layers of hydrocarbons. Modeling calculations of the multi-layer thin films assist in the interpretation of the experimental results and reveal the role of optical interference in masking the aforementioned ammonia spectral feature. The implications of these results for Jupiter's atmosphere will be discussed. Funding from the NSF Planetary Astronomy Program under grant AST-0206270 and from the NASA Outer Planets Research Program under grant NNG06GF37G is gratefully acknowledged. The participation of Anand Oza (Princeton University) was made possible by the NSF Research Experiences for Undergraduates Program under grant PHY-0353745. 1. S. K. Atreya, A.-S. Wong, K. H. Baines, M. H. Wong, T. C. Owen, Planet. Space Science 53, 498 (2005). 2. K. H. Baines, R. W. Carlson, and L. W. Kamp, Icarus 159, 74 (2002). 3. A.-S. Wong, Y. L. Yung, and A. J. Friedson, Geophys. Res. Lett. 30, 1447 (2003).

Studies on Ammonia Spectral Signatures Relevant to Jupiter's Clouds

NASA Astrophysics Data System (ADS)

Oza, A. U.; Marschall, J.; Wong, M. H.; Kalogerakis, K. S.

2006-12-01

Observational evidence and thermochemical models indicate an abundance of ammonia ice clouds in Jupiter's atmosphere. However, spectrally identifiable ammonia ice clouds are found covering less than 1% of Jupiter's atmosphere, notably in turbulent areas [1,2]. Current literature suggests two possible explanations: coating by a hydrocarbon haze and/or photochemical processing ("tanning")[2,3]. We are pursuing a research program investigating the above hypotheses. In the experiments, thin films of ammonia ices are deposited in a cryogenic apparatus, coated with hydrocarbons, and characterized by infrared spectroscopy. The ice films can be irradiated by ultraviolet light to study their photochemistry. The spectroscopic measurements aim to identify the processes that control the optical properties of the ice mixtures and quantify their dependence on the identity of the coating, the temperature, and the ice composition. We have observed a consistent suppression of the ammonia absorption feature at 3 μm with coverage by thin layers of hydrocarbons. Modeling calculations of the multi-layer thin films assist in the interpretation of the experimental results and reveal the role of optical interference in masking the aforementioned ammonia spectral feature. The implications of these results for Jupiter's atmosphere will be discussed. Funding from the NSF Planetary Astronomy Program under grant AST-0206270 and from the NASA Outer Planets Research Program under grant NNG06GF37G is gratefully acknowledged. The participation of Anand Oza (Princeton University) was made possible by the NSF Research Experiences for Undergraduates Program under grant PHY-0353745. 1. S. K. Atreya, A.-S. Wong, K. H. Baines, M. H. Wong, T. C. Owen, Planet. Space Science 53, 498 (2005). 2. K. H. Baines, R. W. Carlson, and L. W. Kamp, Icarus 159, 74 (2002). 3. A.-S. Wong, Y. L. Yung, and A. J. Friedson, Geophys. Res. Lett. 30, 1447 (2003).

Exponential 6 parameterization for the JCZ3-EOS

DOE Office of Scientific and Technical Information (OSTI.GOV)

McGee, B.C.; Hobbs, M.L.; Baer, M.R.

1998-07-01

A database has been created for use with the Jacobs-Cowperthwaite-Zwisler-3 equation-of-state (JCZ3-EOS) to determine thermochemical equilibrium for detonation and expansion states of energetic materials. The JCZ3-EOS uses the exponential 6 intermolecular potential function to describe interactions between molecules. All product species are characterized by r*, the radius of the minimum pair potential energy, and {var_epsilon}/k, the well depth energy normalized by Boltzmann`s constant. These parameters constitute the JCZS (S for Sandia) EOS database describing 750 gases (including all the gases in the JANNAF tables), and have been obtained by using Lennard-Jones potential parameters, a corresponding states theory, pure liquid shockmore » Hugoniot data, and fit values using an empirical EOS. This database can be used with the CHEETAH 1.40 or CHEETAH 2.0 interface to the TIGER computer program that predicts the equilibrium state of gas- and condensed-phase product species. The large JCZS-EOS database permits intermolecular potential based equilibrium calculations of energetic materials with complex elemental composition.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ali T-Raissi

The aim of this work was to assess issues of cost, and performance associated with the production and storage of hydrogen via following three feedstocks: sub-quality natural gas (SQNG), ammonia (NH{sub 3}), and water. Three technology areas were considered: (1) Hydrogen production utilizing SQNG resources, (2) Hydrogen storage in ammonia and amine-borane complexes for fuel cell applications, and (3) Hydrogen from solar thermochemical cycles for splitting water. This report summarizes our findings with the following objectives: Technoeconomic analysis of the feasibility of the technology areas 1-3; Evaluation of the hydrogen production cost by technology areas 1; and Feasibility of ammoniamore » and/or amine-borane complexes (technology areas 2) as a means of hydrogen storage on-board fuel cell powered vehicles. For each technology area, we reviewed the open literature with respect to the following criteria: process efficiency, cost, safety, and ease of implementation and impact of the latest materials innovations, if any. We employed various process analysis platforms including FactSage chemical equilibrium software and Aspen Technologies AspenPlus and HYSYS chemical process simulation programs for determining the performance of the prospective hydrogen production processes.« less

Real-air data reduction procedures based on flow parameters measured in the test section of supersonic and hypersonic facilities

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1972-01-01

Data-reduction procedures for determining free stream and post-normal shock kinetic and thermodynamic quantities are derived. These procedures are applicable to imperfect real air flows in thermochemical equilibrium for temperatures to 15 000 K and a range of pressures from 0.25 N/sq m to 1 GN/sq m. Although derived primarily to meet the immediate needs of the 6-inch expansion tube, these procedures are applicable to any supersonic or hypersonic test facility where combinations of three of the following flow parameters are measured in the test section: (1) Stagnation pressure behind normal shock; (2) freestream static pressure; (3) stagnation point heat transfer rate; (4) free stream velocity; (5) stagnation density behind normal shock; and (6) free stream density. Limitations of the nine procedures and uncertainties in calculated flow quantities corresponding to uncertainties in measured input data are discussed. A listing of the computer program is presented, along with a description of the inputs required and a sample of the data printout.

Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.

2004-03-29

In the present work, it has been the aim to examine extraction efficiencies of nine proton-ionizable alcohols (HAs) in 1-octanol and to identify both the controlling equilibria and predominant species involved in the extraction process within a thermochemical model. Distribution ratios for sodium (DNa) extraction were measured as a function of organic-phase HA and aqueous-phase NaOH molarity at 25 °C. Extraction efficiency follows the expected order of acidity of the HAs, 4-(tert-octyl) phenol (HA 1a) and 4-noctyl- a,a-bis-(trifluoromethyl)benzyl alcohol (HA 2a) being the most efficient extractants among the compounds tested. By use of the equilibrium-modeling program SXLSQI, a model formore » the extraction of NaOH has been advanced based on an ion-pair extraction by the diluent to give organic-phase Na+OH- and corresponding free ions and cation exchange by the weak acids to form monomeric organic-phase Na+A- and corresponding free organic-phase ions.« less

Coal Technology Program progress report, March 1976

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

Shakedown tests of the bench-scale hydrocarbonization system were successfully completed. Wyodak coal was fed to the reactor at a rate of 9.9 lb/hr where it was hydrocarbonized at 1050/sup 0/F under 20-atm hydrogen pressure. Laboratory results including settling tests, bench-scale settling tests, and sample ageing tests were continued. Two of ten compounds tested with the laboratory-scale apparatus were effective in increasing settling rates of solids in Solvent Refined Coal unfiltered oil, but bench-scale tests failed to show any improvements in the settling rate over the untreated SRC-UFO. Analytical chemistry efforts involved the removal and concentration of organic components in by-productmore » waters from fossil fuel conversion processes. A sephadex gel is being used to achieve hydrophilic-lipophilic separations in organic mixtures as a step in the analysis of fossil fuel related materials. Engineering Evaluations of the Synthiol and Hydrocarbonization Processes continued with the Synthiol process flow diagrams, heat and material balances, and utilities requirements being completed. Inspection techniques were developed for wear- and process-resistant coatings. Orders were placed for the Incoloy 800 tubing and a smaller quantity of Inconel 600 tubing for the tube matrix in the coal-fueled MIUS fluidized bed. An engineering feasibility review of General Atomic's proposal to ERDA for a bench-scale test program on thermochemical water splitting for hydrogen production was completed. (auth)« less

Analysis and comparison of biomass pyrolysis/gasification condensates: Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elliott, D.C.

1986-06-01

This report provides results of chemical and physical analysis of condensates from eleven biomass gasification and pyrolysis systems. The samples were representative of the various reactor configurations being researched within the Department of Energy, Biomass Thermochemical Conversion program. The condensates included tar phases and aqueous phases. The analyses included gross compositional analysis (elemental analysis, ash, moisture), physical characterization (pour point, viscosity, density, heat of combustion, distillation), specific chemical analysis (gas chromatography/mass spectrometry, infrared spectrophotometry, proton and carbon-13 nuclear magnetic resonance spectrometry) and biological activity (Ames assay and mouse skin tumorigenicity tests). These results are the first step of a longermore » term program to determine the properties, handling requirements, and utility of the condensates recovered from biomass gasification and pyrolysis. The analytical data demonstrates the wide range of chemical composition of the organics recovered in the condensates and suggests a direct relationship between operating temperature and chemical composition of the condensates. A continuous pathway of thermal degradation of the tar components as a function of temperature is proposed. Variations in the chemical composition of the organic components in the tars are reflected in the physical properties of tars and phase stability in relation to water in the condensate. The biological activity appears to be limited to the tars produced at high temperatures. 56 refs., 25 figs., 21 tabs.« less

Coal technology program progress report, February 1976

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

Final testing of the 20-atm bench-scale system is underway in preparation for experiments with hydrogen. Laboratory-scale testing of a number of inexpensive pure compounds to improve the settling rate of solids in Solvent Refined Coal (SRC) unfiltered oil (UFO), bench-scale testing of the effect of the Tretolite additive on settling, and characterization tests on a new sample of UFO from the PAMCO-SRC process are reported. Experimental engineering support of an in situ gasification process include low-temperature pyrolyses at exceptionally low heating rates (0.3/sup 0/C/min). Highly pyrophoric chars were consistently produced. Aqueous by-products from coal conversion technologies and oil shale retortingmore » have been analyzed directly to determine major organic components. A report is being prepared discussing various aspects of the engineering evaluations of nuclear process heat for coal. A bench-scale test program on thermochemical water splitting for hydrogen production is under consideration. In the coal-fueled MIUS program, preparations for procurement of tubing for the matrix in the fluidized-bed furnace and for fabrication of the furnace continued. Analyses of the AiResearch gas turbine and recuperator under coal-fueled MIUS operating conditions are near completion. Process flow diagrams and heat and material balances were completed for most of the units in the synthoil process. Overall utilities requirements were calculated and the coal preparation flowsheets were finalized. For hydrocarbonization, the flowsheet was revised to include additional coal data. Flowsheets were finalized for the acid gas separation and recycle, and the oil-solids separation. (LTN)« less

Research Opportunities Supporting the Vision for Space Exploration from the Transformation of the Former Microgravity Materials Science Program

NASA Technical Reports Server (NTRS)

Clinton, R. G., Jr.; Szofran, Frank; Bassler, Julie A.; Schlagheck, Ronald A.; Cook, Mary Beth

2005-01-01

The Microgravity Materials Science Program established a strong research capability through partnerships between NASA and the scientific research community. With the announcement of the vision for space exploration, additional emphasis in strategic materials science areas was necessary. The President's Commission recognized that achieving its exploration objectives would require significant technical innovation, research, and development in focal areas defined as "enabling technologies." Among the 17 enabling technologies identified for initial focus were: advanced structures, advanced power and propulsion; closed-loop life support and habitability; extravehicular activity systems; autonomous systems and robotics; scientific data collection and analysis, biomedical risk mitigation; and planetary in situ resource utilization. Mission success may depend upon use of local resources to fabricate a replacement part to repair a critical system. Future propulsion systems will require materials with a wide range of mechanical, thermophysical, and thermochemical properties, many of them well beyond capabilities of today's materials systems. Materials challenges have also been identified by experts working to develop advanced life support systems. In responding to the vision for space exploration, the Microgravity Materials Science Program aggressively transformed its research portfolio and focused materials science areas of emphasis to include space radiation shielding; in situ fabrication and repair for life support systems; in situ resource utilization for life support consumables; and advanced materials for exploration, including materials science for space propulsion systems and for life support systems. The purpose of this paper is to inform the scientific community of these new research directions and opportunities to utilize their materials science expertise and capabilities to support the vision for space exploration.

Coupled Radiation-Gasdynamic Solution Method for Hypersonic Shock Layers in Thermochemical Nonequilibrium

DTIC Science & Technology

2011-12-01

Dissertation, North Carolina State University, 1991. Heppenheimer , T. A ., ―Facing the Heat Barrier: a History of Hypersonics,‖ NASA SP- 2007-4232...States Government. This material is declared a work of the U.S. Government and is not subject to copyright protection in the United States...Lofthouse, PhD (Member) Date Accepted: ______________________________ M. U. THOMAS Date Dean, Graduate

Review of the Pyrolysis Platform for Producing Bio-oil and Biochar: Technology, Logistics, and Potential Impacts on Greenhouse Gas Emissions, Water Quality, Soil Quality, and Agricultural Productivity

USDA-ARS?s Scientific Manuscript database

Pyrolysis is a relatively simple, inexpensive, and robust thermochemical technology for transforming biomass into bio-oil, biochar, and syngas. The robust nature of the pyrolysis technology, which allows considerable flexibility in both the type and quality of the biomass feedstock, combined with a ...

Biological Hydrogen Production: Simultaneous Saccharification and Fermentation with Nitrogen and Phosphorus Removal from Wastewater Effluent

DTIC Science & Technology

2010-07-29

bedirectly catalyzed tomonosaccharidesby cellulaseswithout requiring thermochemical pretreatment , aswould typically be required with lignocellulosic ...of a similar process with lignocellulosic biomass, although such biomass would likely require ther- mochemical pretreatment prior to enzymatic...by the automatic addition of 0.1 N NaOH . Total organic carbon (TOC), ammonia nitrogen, nitrate nitrogen, nitrite nitrogen and phosphorus analyses

CuC1 thermochemical cycle for hydrogen production

DOEpatents

Fan, Qinbai [Chicago, IL; Liu, Renxuan [Chicago, IL

2012-01-03

An electrochemical cell for producing copper having a dense graphite anode electrode and a dense graphite cathode electrode disposed in a CuCl solution. An anion exchange membrane made of poly(ethylene vinyl alcohol) and polyethylenimine cross-linked with a cross-linking agent selected from the group consisting of acetone, formaldehyde, glyoxal, glutaraldehyde, and mixtures thereof is disposed between the two electrodes.