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

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.

Status of the DOE /STOR/-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

A pure thermochemical cycle is a system of linked regenerative chemical reactions which accepts only water and heat and produces hydrogen. Thermochemical cycles are potentially a more efficient and cheaper means of producing hydrogen from water than is the generation of electricity followed by electrolysis. The Energy Storage Systems Division of the Department of Energy is currently funding a national program on thermochemical hydrogen production. The National Aeronautics and Space Administration is responsible for the technical management of this program. The goal is to develop a cycle which can potentially operate with an efficiency greater than 40% using a heat source providing a maximum available temperature of 1150 K. A closed bench-scale demonstration of such a cycle would follow. This cycle would be labeled a 'reference cycle' and would serve as a baseline against which future cycles would be compared.

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.

Sea, soil, sky - Testing solar's limits

NASA Astrophysics Data System (ADS)

Hopkinson, J.

1981-12-01

The potentials and actualities of large scale biomass, ocean thermal, and satellite solar power systems are discussed. Biomass is an energy already on-line in installations ranging from home-sized wood-burning stoves to utility sized generators fueled by sawdust and forest residue. Uses of wheat straw, fast-growing trees such as eucalyptus and alder, and euphorbia as biofuels are examined, noting restrictions imposed by land use limitations and the necessity for genetic engineering for more suitable plants. Pyrolysis and thermochemical gasification of biomass to form gaseous, solid, and liquid fuels are explored, and mention is made of utility refuse and sewage incineration for power generation. OTEC, satellite solar power systems, and tidal generator plants are considered as promising for further investigation and perhaps useful in limited applications, while solar pond power plants require extremely large areas to be effective.

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...

Methods and systems for producing syngas

DOEpatents

Hawkes, Grant L; O& #x27; Brien, James E; Stoots, Carl M; Herring, J. Stephen; McKellar, Michael G; Wood, Richard A; Carrington, Robert A; Boardman, Richard D

2013-02-05

Methods and systems are provided for producing syngas utilizing heat from thermochemical conversion of a carbonaceous fuel to support decomposition of at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells. Simultaneous decomposition of carbon dioxide and water or steam by one or more solid-oxide electrolysis cells may be employed to produce hydrogen and carbon monoxide. A portion of oxygen produced from at least one of water and carbon dioxide using one or more solid-oxide electrolysis cells is fed at a controlled flow rate in a gasifier or combustor to oxidize the carbonaceous fuel to control the carbon dioxide to carbon monoxide ratio produced.

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.

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.

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.

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.

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.

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)

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.

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...

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...

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)

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 ...

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.

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.

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.

Using reflection time-of-flight mass spectrometer techniques to investigate cluster dynamics and bonding

NASA Astrophysics Data System (ADS)

Wei, Shiqing; Castleman, A. W., Jr.

1994-02-01

Lase based time-of-flight mass spectrometer systems affixed with reflectrons are valuable tools for investigating cluster dynamics and reactions, spectroscopy and structures. Utilizing the reflectron time-of-flight mass spectrometer techniques, both decay fractions and kinetic energy releases of metastable cluster ions can be measured with high precision. By applying related theoretical models, the desired thermochemical values of metastable species can be deduced, which are otherwise very difficult to obtain. Several examples are discussed with attention focused on ammonia as a test case for hydrogen bond systems, and xenon for weaker van der Waals clusters. A brief overview of applications to investigating solvation effects on reactions and structures, delayed electron transfer and ionization through intracluster Penning ionization is also given.

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.

Non-equilibrium chemistry in the solar nebula and early solar system: Implications for the chemistry of comets

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr.

1989-01-01

Theoretical models of solar nebula and early solar system chemistry which take into account the interplay between chemical, physical, and dynamical processes have great utility for deciphering the origin and evolution of the abundant chemically reactive volatiles (H, O, C, N, S) observed in comets. In particular, such models are essential for attempting to distinguish between presolar and solar nebula products and for quantifying the nature and duration of nebular and early solar system processing to which the volatile constituents of comets have been subjected. The diverse processes and energy sources responsible for chemical processing in the solar nebula and early solar system are discussed. The processes considered include homogeneous and heterogeneous thermochemical and photochemical reactions, and disequilibration resulting from fluid transport, condensation, and cooling whenever they occur on timescales shorter than those for chemical reactions.

The SERI solar energy storage program

NASA Technical Reports Server (NTRS)

Copeland, R. J.; Wright, J. D.; Wyman, C. E.

1980-01-01

In support of the DOE thermal and chemical energy storage program, the solar energy storage program (SERI) provides research on advanced technologies, systems analyses, and assessments of thermal energy storage for solar applications in support of the Thermal and Chemical Energy Storage Program of the DOE Division of Energy Storage Systems. Currently, research is in progress on direct contact latent heat storage and thermochemical energy storage and transport. Systems analyses are being performed of thermal energy storage for solar thermal applications, and surveys and assessments are being prepared of thermal energy storage in solar applications. A ranking methodology for comparing thermal storage systems (performance and cost) is presented. Research in latent heat storage and thermochemical storage and transport is reported.

Mid-infrared laser absorption tomography for quantitative 2D thermochemistry measurements in premixed jet flames

NASA Astrophysics Data System (ADS)

Wei, Chuyu; Pineda, Daniel I.; Paxton, Laurel; Egolfopoulos, Fokion N.; Spearrin, R. Mitchell

2018-06-01

A tomographic laser absorption spectroscopy technique, utilizing mid-infrared light sources, is presented as a quantitative method to spatially resolve species and temperature profiles in small-diameter reacting flows relevant to combustion systems. Here, tunable quantum and interband cascade lasers are used to spectrally resolve select rovibrational transitions near 4.98 and 4.19 μm to measure CO and {CO2}, respectively, as well as their vibrational temperatures, in piloted premixed jet flames. Signal processing methods are detailed for the reconstruction of axial and radial profiles of thermochemical structure in a canonical ethylene-air jet flame. The method is further demonstrated to quantitatively distinguish between different turbulent flow conditions.

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.

Thermochemical Users Facility | Bioenergy | NREL

Science.gov Websites

collaborate on research and development efforts or to use our equipment to test their materials and processes NREL's thermochemical process integration, scale-up, and piloting research. Schematic diagram of NRELs about NREL's thermochemical process integration, scale-up, and piloting research. Thermochemical

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.

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

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.

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.

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.

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.

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

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.

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.

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.

A Commercialization Roadmap for Carbon-Negative Energy Systems

NASA Astrophysics Data System (ADS)

Sanchez, D.

2016-12-01

The Intergovernmental Panel on Climate Change (IPCC) envisages the need for large-scale deployment of net-negative CO2 emissions technologies by mid-century to meet stringent climate mitigation goals and yield a net drawdown of atmospheric carbon. Yet there are few commercial deployments of BECCS outside of niche markets, creating uncertainty about commercialization pathways and sustainability impacts at scale. This uncertainty is exacerbated by the absence of a strong policy framework, such as high carbon prices and research coordination. Here, we propose a strategy for the potential commercial deployment of BECCS. This roadmap proceeds via three steps: 1) via capture and utilization of biogenic CO2 from existing bioenergy facilities, notably ethanol fermentation, 2) via thermochemical co-conversion of biomass and fossil fuels, particularly coal, and 3) via dedicated, large-scale BECCS. Although biochemical conversion is a proven first market for BECCS, this trajectory alone is unlikely to drive commercialization of BECCS at the gigatonne scale. In contrast to biochemical conversion, thermochemical conversion of coal and biomass enables large-scale production of fuels and electricity with a wide range of carbon intensities, process efficiencies and process scales. Aside from systems integration, primarily technical barriers are involved in large-scale biomass logistics, gasification and gas cleaning. Key uncertainties around large-scale BECCS deployment are not limited to commercialization pathways; rather, they include physical constraints on biomass cultivation or CO2 storage, as well as social barriers, including public acceptance of new technologies and conceptions of renewable and fossil energy, which co-conversion systems confound. Despite sustainability risks, this commercialization strategy presents a pathway where energy suppliers, manufacturers and governments could transition from laggards to leaders in climate change mitigation efforts.

Gasification: An alternative solution for energy recovery and utilization of vegetable market waste.

PubMed

Narnaware, Sunil L; Srivastava, Nsl; Vahora, Samir

2017-03-01

Vegetables waste is generally utilized through a bioconversion process or disposed of at municipal landfills, dumping sites or dumped on open land, emitting a foul odor and causing health hazards. The presents study deals with an alternative way to utilize solid vegetable waste through a thermochemical route such as briquetting and gasification for its energy recovery and subsequent power generation. Briquettes of 50 mm diameter were produced from four different types of vegetable waste. The bulk density of briquettes produced was increased 10 to 15 times higher than the density of the dried vegetable waste in loose form. The lower heating value (LHV) of the briquettes ranged from 10.26 MJ kg -1 to 16.60 MJ kg -1 depending on the type of vegetable waste. The gasification of the briquettes was carried out in an open core downdraft gasifier, which resulted in syngas with a calorific value of 4.71 MJ Nm -3 at the gasification temperature between 889°C and 1011°C. A spark ignition, internal combustion engine was run on syngas and could generate a maximum load up to 10 kW e . The cold gas efficiency and the hot gas efficiency of the gasifier were measured at 74.11% and 79.87%, respectively. Energy recovery from the organic vegetable waste was possible through a thermochemical conversion route such as briquetting and subsequent gasification and recovery of the fuel for small-scale power generation.

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.

Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-wen

2017-04-01

Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.

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.

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

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.

The Conceptual Design of an Integrated Nuclearhydrogen Production Plant Using the Sulfur Cycle Water Decomposition System

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

A hydrogen production plant was designed based on a hybrid electrolytic-thermochemical process for decomposing water. The sulfur cycle water decomposition system is driven by a very high temperature nuclear reactor that provides 1,283 K helium working gas. The plant is sized to approximately ten million standard cubic meters per day of electrolytically pure hydrogen and has an overall thermal efficiently of 45.2 percent. The economics of the plant were evaluated using ground rules which include a 1974 cost basis without escalation, financing structure and other economic factors. Taking into account capital, operation, maintenance and nuclear fuel cycle costs, the cost of product hydrogen was calculated at $5.96/std cu m for utility financing. These values are significantly lower than hydrogen costs from conventional water electrolysis plants and competitive with hydrogen from coal gasification plants.

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.

Thermochemical cycle analysis using linked CECS72 and HYDRGN computer programs

NASA Technical Reports Server (NTRS)

Donovan, L. F.

1977-01-01

A combined thermochemical cycle analysis computer program was designed. Input to the combined program is the same as input to the thermochemical cycle analysis program except that the extent of the reactions need not be specified. The combined program is designed to be run interactively from a computer time-sharing terminal. This mode of operation allows correction or modification of the cycle to take place during cycle analysis. A group of 13 thermochemical cycles was used to test the combined program.

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.

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)

A Review: Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2013-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing. and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and carbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes.

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

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

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).

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.

Corrosion Considerations for Thermochemical Biomass Liquefaction Process Systems in Biofuel Production

NASA Astrophysics Data System (ADS)

Brady, M. P.; Keiser, J. R.; Leonard, D. N.; Whitmer, L.; Thomson, J. K.

2014-12-01

Thermochemical liquefaction processing of biomass to produce bio-derived fuels (e.g., gasoline, jet fuel, diesel, home heating oil, etc.) is of great recent interest as a renewable energy source. Approaches under investigation include direct liquefaction, hydrothermal liquefaction, hydropyrolysis, fast pyrolysis, etc., to produce energy dense liquids that can be utilized as produced or further processed to provide products of higher value. An issue with bio-oils is that they tend to contain significant concentrations of organic oxygenates, including acids, which make the bio-oil a potential source of corrosion issues in transport, storage, and use. Efforts devoted to modified/further processing of bio-oils to make them less corrosive are currently being widely pursued. Another issue that must also be addressed in bio-oil liquefaction is potential corrosion issues in the process equipment. Depending on the specific process, bio-oil liquefaction production temperatures are typically in the 300-600°C range, and the process environment can contain aggressive sulfur and halide species from both the biomass used and/or process additives. Detailed knowledge of the corrosion resistance of candidate process equipment alloys in these bio-oil production environments is currently lacking. This paper summarizes recent, ongoing efforts to assess the extent of corrosion of bio-oil process equipment, with the ultimate goal of providing a basis for the selection of the lowest cost alloy grades capable of providing the long-term corrosion resistance needed for future bio-oil production plants.

Corrosion considerations for thermochemical biomass liquefaction process systems in biofuel production

DOE PAGES

Brady, Michael P.; Keiser, James R.; Leonard, Donovan N.; ...

2014-11-11

Thermochemical liquifaction processing of biomass to produce bio-derived fuels (e.g. gasoline, jet fuel, diesel, home heating oil, etc.) is of great recent interest as a renewable energy source. Approaches under investigation include direct liquefaction, hydrothermal liquefaction, hydropyrolysis, fast pyrolysis, etc. to produce energy dense liquids that can be utilized as produced or further processed to provide products of higher value. An issue with bio-oils is that they tend to contain significant concentrations of organic compounds, which make the bio-oil acidic and a potential source of corrosion issues in in transport, storage, and use. Efforts devoted to modified/further processing of bio-oilsmore » to make them less corrosive are currently being widely pursued. Another aspect that must also be addressed is potential corrosion issues in the bio-oil liquefaction process equipment itself. Depending on the specific process, bio-oil liquefaction production temperatures can reach up to 400-600 °C, and involve the presence of aggressive sulfur, and halide species from both the biomass used and/or process additives. Detailed knowledge of the corrosion resistance of candidate process equipment alloys in these bio-oil production environments is currently lacking. Lastly, this paper summarizes our recent, ongoing efforts to assess the extent to which corrosion of bio-oil process equipment may be an issue, with the ultimate goal of providing the basis to select the lowest cost alloy grades capable of providing the long-term corrosion resistance needed for future bio-oil production plants.« less

Method for Hot Real-Time Sampling of Pyrolysis Vapors

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

Pomeroy, Marc D

Biomass Pyrolysis has been an increasing topic of research, in particular as a replacement for crude oil. This process utilizes moderate temperatures to thermally deconstruct the biomass which is then condensed into a mixture of liquid oxygenates to be used as fuel precursors. Pyrolysis oils contain more than 400 compounds, up to 60 percent of which do not re-volatilize for subsequent chemical analysis. Vapor chemical composition is also complicated as additional condensation reactions occur during the condensation and collection of the product. Due to the complexity of the pyrolysis oil, and a desire to catalytically upgrade the vapor composition beforemore » condensation, online real-time analytical techniques such as Molecular Beam Mass Spectrometry (MBMS) are of great use. However, in order to properly sample hot pyrolysis vapors, many challenges must be overcome. Sampling must occur within a narrow range of temperatures to reduce product composition changes from overheating or partial condensation or plugging of lines from condensed products. Residence times must be kept at a minimum to reduce further reaction chemistries. Pyrolysis vapors also form aerosols that are carried far downstream and can pass through filters resulting in build-up in downstream locations. The co-produced bio-char and ash from the pyrolysis process can lead to plugging of the sample lines, and must be filtered out at temperature, even with the use of cyclonic separators. A practical approach for considerations and sampling system design, as well as lessons learned are integrated into the hot analytical sampling system of the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU) to provide industrially relevant demonstrations of thermochemical transformations of biomass feedstocks at the pilot scale.« less

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.

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.…

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

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

Electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-01-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

Electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Sammells, Anthony F.; Semkow, Krystyna W.

1987-09-01

A high temperature electrolytic cell which simultaneously generates oxygen at the anode and liquid alkali metals at the cathode is electrochemically characterized. The electrolytic technology being investigated utilizes the oxygen vacancy conducting solid electrolyte, yttria stabilized zirconia, which effectively separates the oxygen evolving (at La0.89Sr0.10MnO3) and alkali metal (Li, Na) reducing (from a molten salt at either Pt or FeSi2) half cell reactions. In the finally engineered cell liquid alkali metal would be continuously removed from the cathode compartment and used as an effective reductant for the direct thermochemical refining of lunar ores to their metallic state with simultaneous oxidation of the alkali metal to its oxide. The alkali metal oxide would then be reintroduced into the electrolytic cell to complete the overall system cycle.

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.

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...

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.

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.

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

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.

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

Prospects for energy recovery during hydrothermal and biological processing of waste biomass.

PubMed

Gerber Van Doren, Léda; Posmanik, Roy; Bicalho, Felipe A; Tester, Jefferson W; Sills, Deborah L

2017-02-01

Thermochemical and biological processes represent promising technologies for converting wet biomasses, such as animal manure, organic waste, or algae, to energy. To convert biomass to energy and bio-chemicals in an economical manner, internal energy recovery should be maximized to reduce the use of external heat and power. In this study, two conversion pathways that couple hydrothermal liquefaction with anaerobic digestion or catalytic hydrothermal gasification were compared. Each of these platforms is followed by two alternative processes for gas utilization: 1) combined heat and power; and 2) combustion in a boiler. Pinch analysis was applied to integrate thermal streams among unit processes and improve the overall system efficiency. A techno-economic analysis was conducted to compare the feasibility of the four modeled scenarios under different market conditions. Our results show that a systems approach designed to recover internal heat and power can reduce external energy demands and increase the overall process sustainability. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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

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.

Using Pyrolysis and its Bioproducts to Help Close the Loop in Sustainable Life Support Systems

NASA Technical Reports Server (NTRS)

McCoy, LaShelle E.

2012-01-01

The next step in human exploration of space is beyond low Earth orbit and possibly to sites such as the Moon and Mars. Resupply of critical life support components for missions such as these are difficult or impossible. Life support processes for closing the loop of water, oxygen and carbon have to be identified .. Currently, there are many technologies proposed for terrestrial missions for waste, water, air processing and the creation of consumables. There are a variety of different approaches, but few address all of these issues simultaneously. One candidate is pyrolysis; a method where waste streams can be heated in the absence of oxygen to undergo a thermochemical conversion producing a series of bioproducts. Bioproducts like biochar made from non-edible biomass and human solid waste can possibly provide valuable benefits such as waste reduction, regolith fertilization for increased food production, and become a consumable for water processing and air revitalization systems. Syngas containing hydrogen, carbon monoxide and cbon dioxide, can be converted to methane and dimethyl ether to create propellants. Bio-oils can be utilized as a heating fuel or fed to bioreactors that utilize oil-eating microbes. Issues such as carbon sequestration and subsequent carbon balance of the closed system and identifying ideal process methods to achieve the highest quality products, whilst being energy friendly, will also be addressed.

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

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.

Method for Hot Real-Time Sampling of Gasification Products

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

Pomeroy, Marc D

The Thermochemical Process Development Unit (TCPDU) at the National Renewable Energy Laboratory (NREL) is a highly instrumented half-ton/day pilot scale plant capable of demonstrating industrially relevant thermochemical technologies from lignocellulosic biomass conversion, including gasification. Gasification creates primarily Syngas (a mixture of Hydrogen and Carbon Monoxide) that can be utilized with synthesis catalysts to form transportation fuels and other valuable chemicals. Biomass derived gasification products are a very complex mixture of chemical components that typically contain Sulfur and Nitrogen species that can act as catalysis poisons for tar reforming and synthesis catalysts. Real-time hot online sampling techniques, such as Molecular Beammore » Mass Spectrometry (MBMS), and Gas Chromatographs with Sulfur and Nitrogen specific detectors can provide real-time analysis providing operational indicators for performance. Sampling typically requires coated sampling lines to minimize trace sulfur interactions with steel surfaces. Other materials used inline have also shown conversion of sulfur species into new components and must be minimized. Sample line Residence time within the sampling lines must also be kept to a minimum to reduce further reaction chemistries. Solids from ash and char contribute to plugging and must be filtered at temperature. Experience at NREL has shown several key factors to consider when designing and installing an analytical sampling system for biomass gasification products. They include minimizing sampling distance, effective filtering as close to source as possible, proper line sizing, proper line materials or coatings, even heating of all components, minimizing pressure drops, and additional filtering or traps after pressure drops.« less

Regenerative Carbonate-Based Thermochemical Energy Storage System for Concentrating Solar Power

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

Gangwal, Santosh; Muto, Andrew

Southern Research has developed a thermochemical energy storage (TCES) technology that utilizes the endothermic-exothermic reversible carbonation of calcium oxide (lime) to store thermal energy at high-temperatures, such as those achieved by next generation concentrating solar power (CSP) facilities. The major challenges addressed in the development of this system include refining a high capacity, yet durable sorbent material and designing a low thermal resistance low-cost heat exchanger reactor system to move heat between the sorbent and a heat transfer fluid under conditions relevant for CSP operation (e.g., energy density, reaction kinetics, heat flow). The proprietary stabilized sorbent was developed by Precisionmore » Combustion, Inc. (PCI). A factorial matrix of sorbent compositions covering the design space was tested using accelerated high throughput screening in a thermo-gravimetric analyzer. Several promising formulations were selected for more thorough evaluation and one formulation with high capacity (0.38 g CO 2/g sorbent) and durability (>99.7% capacity retention over 100 cycles) was chosen as a basis for further development of the energy storage reactor system. In parallel with this effort, a full range of currently available commercial and developmental heat exchange reactor systems and sorbent loading methods were examined through literature research and contacts with commercial vendors. Process models were developed to examine if a heat exchange reactor system and balance of plant can meet required TCES performance and cost targets, optimizing tradeoffs between thermal performance, exergetic efficiency, and cost. Reactor types evaluated included many forms, from microchannel reactor, to diffusion bonded heat exchanger, to shell and tube heat exchangers. The most viable design for application to a supercritical CO 2 power cycle operating at 200-300 bar pressure and >700°C was determined to be a combination of a diffusion bonded heat exchanger with a shell and tube reactor. A bench scale reactor system was then designed and constructed to test sorbent performance under more commercially relevant conditions. This system utilizes a tube-in tube reactor design containing approximately 250 grams sorbent and is able to operate under a wide range of temperature, pressure and flow conditions as needed to explore system performance under a variety of operating conditions. A variety of sorbent loading methods may be tested using the reactor design. Initial bench test results over 25 cycles showed very high sorbent stability (>99%) and sufficient capacity (>0.28 g CO 2/g sorbent) for an economical commercial-scale system. Initial technoeconomic evaluation of the proposed storage system show that the sorbent cost should not have a significant impact on overall system cost, and that the largest cost impacts come from the heat exchanger reactor and balance of plant equipment, including compressors and gas storage, due to the high temperatures for sCO 2 cycles. Current estimated system costs are $47/kWhth based on current material and equipment cost estimates.« less

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.

Oil Palm Empty Fruit Bunches (OPEFB): Existing Utilization and Current Trends Bio Refinery in Indonesia

NASA Astrophysics Data System (ADS)

Rame

2018-02-01

In a future carbon-constrained global economy, the use of fossil fuels will be restricted. Biomass resources will be increased demand for renewable products. Oil Palm Empty Fruit Bunches (OPEFB) can be used as lignocellulose feedstock. The production of biofuels from lignocellulose feedstock can be achieved through biochemical or thermo-chemical routes. OPEFB contain chemical blocks of cellulose, hemicellulose and lignocellulose. Due to these substances, OPEFB can be converted into bio-products and chemical. Special attention to biorefinery approach that is present at relatively high potential in bio-products such as polymers, nutraceuticals, chemical building blocks, biofuels, and bioenergy. Different utilization types were considered and reviewed, and the most common and efficient process were discussed. In general, there is no single product which could be considered a solution to the utilization of managing OPEFB - in this review a number of product are more economic, effective and environmentally friendly.

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.

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.

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.

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)

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.

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...

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

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

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

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

Scalable and Tunable Carbide-Phosphide Composite Catalyst System for the Thermochemical Conversion of Biomass

DOE PAGES

Regmi, Yagya; Rogers, Bridget; Labbe, Nicole; ...

2017-07-13

We have prepared composite materials of hexagonal nickel phosphide and molybdenum carbide (Mo2C) utilizing a simple and scalable two-stage synthesis method comprised of carbothermic reduction followed by hydrothermal incubation. We observe the monophasic hexagonal phosphide Ni2P in the composite at low phosphide-to-carbide (P:C) ratios. Upon increasing the proportion of P:C, the carbide surface becomes saturated, and we detect the emergence of a second hexagonal nickel phosphide phase (Ni5P4) upon annealing. We demonstrate that vapor-phase upgrading (VPU) of whole biomass via catalytic fast pyrolysis is achievable using the composite material as a catalyst, and we monitor the resulting product slates usingmore » pyrolysis gas chromatography/mass spectrometry. Our analysis of the product vapors indicates that variation of the P:C molar ratio in the composite material affords product slates of varying complexity and composition, which is indicated by the number of products and their relative proportions in the product slate. Our results demonstrate that targeted vapor product composition can be obtained, which can potentially be utilized to tune the composition of the bio-oil downstream.« less

2011 Biomass Program Platform Peer Review. Thermochemical Conversion

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

Grabowski, Paul E.

This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the 2011 U.S. Department of Energy Biomass Program’s Thermochemical Conversion Platform Review meeting.

Thermoelectrochemical system and method

DOEpatents

Ludwig, F.A.; Townsend, C.W.; Eliash, B.M.

1995-11-28

A thermal electrochemical system is described in which an electrical current is generated between a cathode immersed in a concentrated aqueous solution of phosphoric acid and an anode immersed in a molten salt solution of ammonium phosphate and monohydric ammonium phosphate. Reactants consumed at the electrodes during the electrochemical reaction are thermochemically regenerated and recycled to the electrodes to provide continuous operation of the system. 5 figs.

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.

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...

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.

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.

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...

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.

Application of thermochemical modeling to aircraft interior polymeric materials

DOT National Transportation Integrated Search

1982-06-01

This report summarizes the results from a twelve-month study of the feasibility of applying certain basic concepts in the thermochemical modeling to aircraft cabin fire safety. The concepts developed earlier on a NASA-sponsored program were applied t...

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.

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.

Renewable hydrogen production via thermochemical/electrochemical coupling

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

Ambrosini, Andrea; Babiniec, Sean Michael; Miller, James E.

A coupled electrochemical/thermochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this cycle leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy only needs to be partially, but not fully, capable of splitting steam to produce hydrogen. To complete the process, a proton-conducting membrane is driven to separate hydrogen as it is produced, thus shifting the thermodynamics toward further hydrogen production. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material ismore » reduced, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam-splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production methods. This Exploratory Express LDRD involved assessing the practical feasibility of the proposed coupled cycle. A test stand was designed and constructed and proton-conducting membranes were synthesized. While the full proof of concept was not achieved, the individual components of the experiment were validated and new capabilities that can be leveraged by a variety of programs were developed.« less

GH51 Arabinofuranosidase and Its Role in the Methylglucuronoarabinoxylan Utilization System in Paenibacillus sp. Strain JDR-2

PubMed Central

Sawhney, Neha

2014-01-01

Methylglucuronoarabinoxylan (MeGAXn) from agricultural residues and energy crops is a significant yet underutilized biomass resource for production of biofuels and chemicals. Mild thermochemical pretreatment of bagasse yields MeGAXn requiring saccharifying enzymes for conversion to fermentable sugars. A xylanolytic bacterium, Paenibacillus sp. strain JDR-2, produces an extracellular cell-associated GH10 endoxylanse (XynA1) which efficiently depolymerizes methylglucuronoxylan (MeGXn) from hardwoods coupled with assimilation of oligosaccharides for further processing by intracellular GH67 α-glucuronidase, GH10 endoxylanase, and GH43 β-xylosidase. This process has been ascribed to genes that comprise a xylan utilization regulon that encodes XynA1 and includes a gene cluster encoding transcriptional regulators, ABC transporters, and intracellular enzymes that convert assimilated oligosaccharides to fermentable sugars. Here we show that Paenibacillus sp. JDR-2 utilized MeGAXn without accumulation of oligosaccharides in the medium. The Paenibacillus sp. JDR-2 growth rate on MeGAXn was 3.1-fold greater than that on oligosaccharides generated from MeGAXn by XynA1. Candidate genes encoding GH51 arabinofuranosidases with potential roles were identified. Following growth on MeGAXn, quantitative reverse transcription-PCR identified a cluster of genes encoding a GH51 arabinofuranosidase (AbfB) and transcriptional regulators which were coordinately expressed along with the genes comprising the xylan utilization regulon. The action of XynA1 on MeGAXn generated arabinoxylobiose, arabinoxylotriose, xylobiose, xylotriose, and methylglucuronoxylotriose. Recombinant AbfB processed arabinoxylooligosaccharides to xylooligosaccharides and arabinose. MeGAXn processing by Paenibacillus sp. JDR-2 may be achieved by extracellular depolymerization by XynA1 coupled to assimilation of oligosaccharides and further processing by intracellular enzymes, including AbfB. Paenibacillus sp. JDR-2 provides a GH10/GH67 system complemented with genes encoding intracellular GH51 arabinofuranosidases for efficient utilization of MeGAXn. PMID:25063665

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.

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.

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

Damage to the microbial cell membrane during pyrolytic sugar utilization and strategies for increasing resistance.

PubMed

Jin, Tao; Rover, Marjorie R; Petersen, Elspeth M; Chi, Zhanyou; Smith, Ryan G; Brown, Robert C; Wen, Zhiyou; Jarboe, Laura R

2017-09-01

Lignocellulosic biomass is an appealing feedstock for the production of biorenewable fuels and chemicals, and thermochemical processing is a promising method for depolymerizing it into sugars. However, trace compounds in this pyrolytic sugar syrup are inhibitory to microbial biocatalysts. This study demonstrates that hydrophobic inhibitors damage the cell membrane of ethanologenic Escherichia coli KO11+lgk. Adaptive evolution was employed to identify design strategies for improving pyrolytic sugar tolerance and utilization. Characterization of the resulting evolved strain indicates that increased resistance to the membrane-damaging effects of the pyrolytic sugars can be attributed to a glutamine to leucine mutation at position 29 of carbon storage regulator CsrA. This single amino acid change is sufficient for decreasing EPS protein production and increasing membrane integrity when exposed to pyrolytic sugars.

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.

Computational Aerothermodynamic Design Issues for Hypersonic Vehicles

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Weilmuenster, K. James; Hamilton, H. Harris, II; Olynick, David R.; Venkatapathy, Ethiraj

1997-01-01

A brief review of the evolutionary progress in computational aerothermodynamics is presented. The current status of computational aerothermodynamics is then discussed, with emphasis on its capabilities and limitations for contributions to the design process of hypersonic vehicles. Some topics to be highlighted include: (1) aerodynamic coefficient predictions with emphasis on high temperature gas effects; (2) surface heating and temperature predictions for thermal protection system (TPS) design in a high temperature, thermochemical nonequilibrium environment; (3) methods for extracting and extending computational fluid dynamic (CFD) solutions for efficient utilization by all members of a multidisciplinary design team; (4) physical models; (5) validation process and error estimation; and (6) gridding and solution generation strategies. Recent experiences in the design of X-33 will be featured. Computational aerothermodynamic contributions to Mars Pathfinder, METEOR, and Stardust (Comet Sample return) will also provide context for this discussion. Some of the barriers that currently limit computational aerothermodynamics to a predominantly reactive mode in the design process will also be discussed, with the goal of providing focus for future research.

Computational Aerothermodynamic Design Issues for Hypersonic Vehicles

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Weilmuenster, K. James; Hamilton, H. Harris, II; Olynick, David R.; Venkatapathy, Ethiraj

2005-01-01

A brief review of the evolutionary progress in computational aerothermodynamics is presented. The current status of computational aerothermodynamics is then discussed, with emphasis on its capabilities and limitations for contributions to the design process of hypersonic vehicles. Some topics to be highlighted include: (1) aerodynamic coefficient predictions with emphasis on high temperature gas effects; (2) surface heating and temperature predictions for thermal protection system (TPS) design in a high temperature, thermochemical nonequilibrium environment; (3) methods for extracting and extending computational fluid dynamic (CFD) solutions for efficient utilization by all members of a multidisciplinary design team; (4) physical models; (5) validation process and error estimation; and (6) gridding and solution generation strategies. Recent experiences in the design of X-33 will be featured. Computational aerothermodynamic contributions to Mars Path finder, METEOR, and Stardust (Comet Sample return) will also provide context for this discussion. Some of the barriers that currently limit computational aerothermodynamics to a predominantly reactive mode in the design process will also be discussed, with the goal of providing focus for future research.

Computational Aerothermodynamic Design Issues for Hypersonic Vehicles

NASA Technical Reports Server (NTRS)

Olynick, David R.; Venkatapathy, Ethiraj

2004-01-01

A brief review of the evolutionary progress in computational aerothermodynamics is presented. The current status of computational aerothermodynamics is then discussed, with emphasis on its capabilities and limitations for contributions to the design process of hypersonic vehicles. Some topics to be highlighted include: (1) aerodynamic coefficient predictions with emphasis on high temperature gas effects; (2) surface heating and temperature predictions for thermal protection system (TPS) design in a high temperature, thermochemical nonequilibrium environment; (3) methods for extracting and extending computational fluid dynamic (CFD) solutions for efficient utilization by all members of a multidisciplinary design team; (4) physical models; (5) validation process and error estimation; and (6) gridding and solution generation strategies. Recent experiences in the design of X-33 will be featured. Computational aerothermodynamic contributions to Mars Pathfinder, METEOR, and Stardust (Comet Sample return) will also provide context for this discussion. Some of the barriers that currently limit computational aerothermodynamics to a predominantly reactive mode in the design process will also be discussed, with the goal of providing focus for future research.

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.

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.

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.

Next-Gen 3: Sequencing, Modeling, and Advanced Biofuels - Final Technical Report

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

Zengler, Karsten; Palsson, Bernhard; Lewis, Nathan

Successful, scalable implementation of biofuels is dependent on the efficient and near complete utilization of diverse biomass sources. One approach is to utilize the large recalcitrant biomass fraction (or any organic waste stream) through the thermochemical conversion of organic compounds to syngas, a mixture of carbon monoxide (CO), carbon dioxide (CO 2), and hydrogen (H 2), which can subsequently be metabolized by acetogenic microorganisms to produce next-gen biofuels. The goal of this proposal was to advance the development of the acetogen Clostridium ljungdahlii as a chassis organism for next-gen biofuel production from cheap, renewable sources and to detail the interconnectivitymore » of metabolism, energy conservation, and regulation of acetogens using next-gen sequencing and next-gen modeling. To achieve this goal we determined optimization of carbon and energy utilization through differential translational efficiency in C. ljungdahlii. Furthermore, we reconstructed a next-generation model of all major cellular processes, such as macromolecular synthesis and transcriptional regulation and deployed this model to predicting proteome allocation, overflow metabolism, and metal requirements in this model acetogen. In addition we explored the evolutionary significance of tRNA operon structure using the next-gen model and determined the optimal operon structure for bioproduction. Our study substantially enhanced the knowledgebaase for chemolithoautotrophs and their potential for advanced biofuel production. It provides next-generation modeling capability, offer innovative tools for genome-scale engineering, and provide novel methods to utilize next-generation models for the design of tunable systems that produce commodity chemicals from inexpensive sources.« less

Next-generation cellulosic ethanol technologies and their contribution to a sustainable Africa

PubMed Central

van Zyl, W. H.; Chimphango, A. F. A.; den Haan, R.; Görgens, J. F.; Chirwa, P. W. C.

2011-01-01

The world is currently heavily dependent on oil, especially in the transport sector. However, rising oil prices, concern about environmental impact and supply instability are among the factors that have led to greater interest in renewable fuel and green chemistry alternatives. Lignocellulose is the only foreseeable renewable feedstock for sustainable production of transport fuels. The main technological impediment to more widespread utilization of lignocellulose for production of fuels and chemicals in the past has been the lack of low-cost technologies to overcome the recalcitrance of its structure. Both biological and thermochemical second-generation conversion technologies are currently coming online for the commercial production of cellulosic ethanol concomitantly with heat and electricity production. The latest advances in biological conversion of lignocellulosics to ethanol with a focus on consolidated bioprocessing are highlighted. Furthermore, integration of cellulosic ethanol production into existing bio-based industries also using thermochemical processes to optimize energy balances is discussed. Biofuels have played a pivotal yet suboptimal role in supplementing Africa's energy requirements in the past. Capitalizing on sub-Saharan Africa's total biomass potential and using second-generation technologies merit a fresh look at the potential role of bioethanol production towards developing a sustainable Africa while addressing food security, human needs and local wealth creation. PMID:22482027

Three-Dimensional Modeling of Flow and Thermochemical Behavior in a Blast Furnace

NASA Astrophysics Data System (ADS)

Shen, Yansong; Guo, Baoyu; Chew, Sheng; Austin, Peter; Yu, Aibing

2015-02-01

An ironmaking blast furnace (BF) is a complex high-temperature moving bed reactor involving counter-, co- and cross-current flows of gas, liquid and solid, coupled with heat and mass exchange and chemical reactions. Two-dimensional (2D) models were widely used for understanding its internal state in the past. In this paper, a three-dimensional (3D) CFX-based mathematical model is developed for describing the internal state of a BF in terms of multiphase flow and the related thermochemical behavior, as well as process indicators. This model considers the intense interactions between gas, solid and liquid phases, and also their competition for the space. The model is applied to a BF covering from the burden surface at the top to the liquid surface in the hearth, where the raceway cavity is considered explicitly. The results show that the key in-furnace phenomena such as flow/temperature patterns and component distributions of solid, gas and liquid phases can be described and characterized in different regions inside the BF, including the gas and liquids flow circumferentially over the 3D raceway surface. The in-furnace distributions of key performance indicators such as reduction degree and gas utilization can also be predicted. This model offers a cost-effective tool to understand and control the complex BF flow and performance.

Design Principles for Metal Oxide Redox Materials for Solar-Driven Isothermal Fuel Production.

PubMed

Michalsky, Ronald; Botu, Venkatesh; Hargus, Cory M; Peterson, Andrew A; Steinfeld, Aldo

2015-04-01

The performance of metal oxides as redox materials is limited by their oxygen conductivity and thermochemical stability. Predicting these properties from the electronic structure can support the screening of advanced metal oxides and accelerate their development for clean energy applications. Specifically, reducible metal oxide catalysts and potential redox materials for the solar-thermochemical splitting of CO 2 and H 2 O via an isothermal redox cycle are examined. A volcano-type correlation is developed from available experimental data and density functional theory. It is found that the energy of the oxygen-vacancy formation at the most stable surfaces of TiO 2 , Ti 2 O 3 , Cu 2 O, ZnO, ZrO 2 , MoO 3 , Ag 2 O, CeO 2 , yttria-stabilized zirconia, and three perovskites scales with the Gibbs free energy of formation of the bulk oxides. Analogously, the experimental oxygen self-diffusion constants correlate with the transition-state energy of oxygen conduction. A simple descriptor is derived for rapid screening of oxygen-diffusion trends across a large set of metal oxide compositions. These general trends are rationalized with the electronic charge localized at the lattice oxygen and can be utilized to predict the surface activity, the free energy of complex bulk metal oxides, and their oxygen conductivity.

Multiparameter spatio-thermochemical probing of flame–wall interactions advanced with coherent Raman imaging

DOE PAGES

Bohlin, Gustav Alexis; Jainski, Christopher; Patterson, Brian D.; ...

2016-08-10

Ultrabroadband coherent anti-Stokes Ra man spectroscopy (CARS) has been developed for one -dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ~7 femtosecond pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ~75 picosecond probe beam provide s excellent spatial sectioning of the probed location. Concurrent detection of N 2, O 2, H 2, CO, CO 2, and CH 4 is demonstrated while high-fidelity flame thermometry is assessed from the N 2 puremore » rotational S-branch in a one-dimensional -CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions ( Φ = 0.83, 1.0 , and 1.2) and Reynolds number = 5,000 is probed as it quenches against a cooled steel side- wall parallel to the flow providing a persistent flame-wall interaction. Here, an imaging resolution of better than 40 μm is achieved across the field -of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ~30 μm of the interface.« less

Multiparameter spatio-thermochemical probing of flame–wall interactions advanced with coherent Raman imaging

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

Bohlin, Gustav Alexis; Jainski, Christopher; Patterson, Brian D.

Ultrabroadband coherent anti-Stokes Ra man spectroscopy (CARS) has been developed for one -dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ~7 femtosecond pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ~75 picosecond probe beam provide s excellent spatial sectioning of the probed location. Concurrent detection of N 2, O 2, H 2, CO, CO 2, and CH 4 is demonstrated while high-fidelity flame thermometry is assessed from the N 2 puremore » rotational S-branch in a one-dimensional -CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions ( Φ = 0.83, 1.0 , and 1.2) and Reynolds number = 5,000 is probed as it quenches against a cooled steel side- wall parallel to the flow providing a persistent flame-wall interaction. Here, an imaging resolution of better than 40 μm is achieved across the field -of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ~30 μm of the interface.« less

Approximate thermochemical tables for some C-H and C-H-O species

NASA Technical Reports Server (NTRS)

Bahn, G. S.

1973-01-01

Approximate thermochemical tables are presented for some C-H and C-H-O species and for some ionized species, supplementing the JANAF Thermochemical Tables for application to finite-chemical-kinetics calculations. The approximate tables were prepared by interpolation and extrapolation of limited available data, especially by interpolations over chemical families of species. Original estimations have been smoothed by use of a modification for the CDC-6600 computer of the Lewis Research Center PACl Program which was originally prepared for the IBM-7094 computer Summary graphs for various families show reasonably consistent curvefit values, anchored by properties of existing species in the JANAF tables.

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.

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

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...

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.

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...

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.

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

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 ).

Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

NASA Astrophysics Data System (ADS)

Lei, Qi; Bader, Roman; Kreider, Peter; Lovegrove, Keith; Lipiński, Wojciech

2017-11-01

We explore the thermodynamic efficiency of a solar-driven combined cycle power system with manganese oxide-based thermochemical energy storage system. Manganese oxide particles are reduced during the day in an oxygen-lean atmosphere obtained with a fluidized-bed reactor at temperatures in the range of 750-1600°C using concentrated solar energy. Reduced hot particles are stored and re-oxidized during night-time to achieve continuous power plant operation. The steady-state mass and energy conservation equations are solved for all system components to calculate the thermodynamic properties and mass flow rates at all state points in the system, taking into account component irreversibilities. The net power block and overall solar-to-electric energy conversion efficiencies, and the required storage volumes for solids and gases in the storage system are predicted. Preliminary results for a system with 100 MW nominal solar power input at a solar concentration ratio of 3000, designed for constant round-the-clock operation with 8 hours of on-sun and 16 hours of off-sun operation and with manganese oxide particles cycled between 750 and 1600°C yield a net power block efficiency of 60.0% and an overall energy conversion efficiency of 41.3%. Required storage tank sizes for the solids are estimated to be approx. 5-6 times smaller than those of state-of-the-art molten salt systems.

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.

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.

FT-IR spectroscopic analyses of 2-(2-furanylmethylene) propanedinitrile

NASA Astrophysics Data System (ADS)

Soliman, H. S.; Eid, Kh. M.; Ali, H. A. M.; El-Mansy, M. A. M.; Atef, S. M.

2013-03-01

In the present work, a computational study for the optimized molecular structural parameters, thermo-chemical parameters, total dipole moment, HOMO-LUMO energy gap and a combined experimental and computational study for FT-IR spectra for 2-(2-furanylmethylene) propanedinitrile have been investigated using B3LYP utilizing 6-31G and 6-311G basis set. Our calculated results showed that the investigated compound possesses a dipole moment of 7.5 D and HOMO-LUMO energy gap of 3.92 eV using B3LYP/6-311G which indicates that our investigated compound is highly applicable for photovoltaic solar cell applications.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge internally heated is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube being internally heated. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and being internally heated. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

Spectroscopic notes of Methyl Red (MR) dye.

PubMed

El-Mansy, M A M; Yahia, I S

2014-09-15

In the present work, a combined experimental and theoretical study on molecular structure and vibrational frequencies of MR were reported. The FT-IR spectrum of MR is recorded in the solid phase. The equilibrium geometries, harmonic vibrational frequencies, thermo-chemical parameters, total dipole moment and HOMO-LUMO energies are calculated by DFT/B3LYP utilizing 6-311G(d,p) basis set. Results showed that MR is highly recommended to be a promising structure for many applications in optoelectronic devices due to its high calculated dipole moment value (7.2 Debye) and lower HOMO-LUMO energy gap of 3.5 eV. Copyright © 2014 Elsevier B.V. All rights reserved.

Survey of hydrogen production and utilization methods. Volume 1: Executive summary

NASA Technical Reports Server (NTRS)

Gregory, D. P.; Pangborn, J. B.; Gillis, J. C.

1975-01-01

The use of hydrogen as a synthetic fuel is considered. Processes for the production of hydrogen are described along with the present and future industrial uses of hydrogen as a fuel and as a chemical feedstock. Novel and unconventional hydrogen-production techniques are evaluated, with emphasis placed on thermochemical and electrolytic processes. Potential uses for hydrogen as a fuel in industrial and residential applications are identified and reviewed in the context of anticipated U.S. energy supplies and demands. A detailed plan for the period from 1975 to 1980 prepared for research on and development of hydrogen as an energy carrier is included.

Thermochemical energy storage with ammonia: Aiming for the sunshot cost target

NASA Astrophysics Data System (ADS)

Lavine, Adrienne S.; Lovegrove, Keith M.; Jordan, Joshua; Anleu, Gabriela Bran; Chen, Chen; Aryafar, Hamarz; Sepulveda, Abdon

2016-05-01

Thermochemical energy storage has the potential to reduce the cost of concentrating solar thermal power. This paper presents recent advances in ammonia-based thermochemical energy storage (TCES), supported by an award from the U.S. Dept. of Energy SunShot program. Advances have been made in three areas: identification of promising approaches for underground containment of the gaseous products of the dissociation reaction, demonstration that ammonia synthesis can be used to generate steam for a supercritical-steam Rankine cycle, and a preliminary design for integration of the endothermic reactors within a tower receiver. Based on these advances, ammonia-based TCES shows promise to meet the 15/kWht SunShot cost target.

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.

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...

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...

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

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

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.

Hydrocarbon Fuel Thermal Performance Modeling based on Systematic Measurement and Comprehensive Chromatographic Analysis

DTIC Science & Technology

2016-07-31

fueled liquid rocket engine, enthalpy is removed from the combustion chamber by a regenerative cooling system comprising a series of passages through... rocket engine, enthalpy is removed from the combustion chamber by a regenerative cooling system comprising a series of passages through which fuel flows...the unprecedented correlation of comprehensive two-dimensional gas chromatographic (GC×GC) rocket fuel data with physical and thermochemical

Integrated solar thermochemical reaction system for steam methane reforming

DOE PAGES

Zheng, Feng; Diver, Rich; Caldwell, Dustin D.; ...

2015-06-05

Solar-aided upgrade of the energy content of fossil fuels, such as natural gas, can provide a near-term transition path towards a future solar-fuel economy and reduce carbon dioxide emission from fossil fuel consumption. Both steam and dry reforming a methane-containing fuel stream have been studied with concentrated solar power as the energy input to drive the highly endothermic reactions but the concept has not been demonstrated at a commercial scale. Under a current project with the U.S. Department of Energy, PNNL is developing an integrated solar thermochemical reaction system that combines solar concentrators with micro- and meso-channel reactors and heatmore » exchangers to accomplish more than 20% solar augment of methane higher heating value. The objective of our three-year project is to develop and prepare for commercialization such solar reforming system with a high enough efficiency to serve as the frontend of a conventional natural gas (or biogas) combined cycle power plant, producing power with a levelized cost of electricity less than 6¢/kWh, without subsidies, by the year 2020. In this paper, we present results from the first year of our project that demonstrated a solar-to-chemical energy conversion efficiency as high as 69% with a prototype reaction system.« less

Co3O4-based honeycombs as compact redox reactors/heat exchangers for thermochemical storage in the next generation CSP plants

NASA Astrophysics Data System (ADS)

Pagkoura, Chrysoula; Karagiannakis, George; Halevas, Eleftherios; Konstandopoulos, Athanasios G.

2016-05-01

Over the last years, several research groups have focused on developing efficient thermochemical heat storage (THS) systems, in-principle capable of being coupled with next generation high temperature Concentrated Solar Power plants. Among systems studied, the Co3O4/CoO redox system is a promising candidate. Currently, research efforts extend beyond basic level identification of promising materials to more application-oriented approaches aiming at validation of THS performance at pilot scale reactors. The present work focuses on the investigation of cobalt oxide based honeycomb structures as candidate reactors/heat exchangers to be employed for such purposes. In the evaluation conducted and presented here, cobalt oxide-based structures with different composition and geometrical characteristics were subjected to redox cycles in the temperature window between 800 and 1000°C under air flow. Basic aspects related to redox performance of each system are briefly discussed but the main focus lies on the evaluation of the segments structural stability after multi-cyclic operation. The latter is based on macroscopic visual observation and also supplemented by pre- (i.e. fresh samples) and post-characterization (i.e. after long term exposure) of extruded honeycombs via combined mercury porosimetry and SEM analysis.

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.

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...

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.

Process of producing liquid hydrocarbon fuels from biomass

DOEpatents

Kuester, James L.

1987-07-07

A continuous thermochemical indirect liquefaction process to convert various biomass materials into diesel-type transportation fuels which fuels are compatible with current engine designs and distribution systems comprising feeding said biomass into a circulating solid fluidized bed gasification system to produce a synthesis gas containing olefins, hydrogen and carbon monoxide and thereafter introducing the synthesis gas into a catalytic liquefaction system to convert the synthesis gas into liquid hydrocarbon fuel consisting essentially of C.sub.7 -C.sub.17 paraffinic hydrocarbons having cetane indices of 50+.

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.

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

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…

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.

Titanium-alloy, metallic-fluid heat pipes for space service

NASA Technical Reports Server (NTRS)

Morris, J. F.

1979-01-01

Reactivities of titanium limit its long-term terrestrial use for unprotected heat-pipe envelopes to about 870 K (1100 F). But this external thermochemical limitation disappears when considerations shift to space applications. In such hard-vacuum utilization much higher operating temperatures are possible. Primary restrictions in space environment result from vaporization, thermal creep, and internal compatibilities. Unfortunately, a respected head-pipe reference indicates that titanium is compatible only with cesium from the alkali-metal working-fluid family. This problem and others are subjects of the present paper which advocates titanium-alloy, metallic-fluid heat pipes for long-lived, weight-effective space service between 500 and 1300 K (440 and 1880 F).

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.

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.

Status of the DOE (STOR)-sponsored national program on hydrogen production from water via thermochemical cycles

NASA Technical Reports Server (NTRS)

Baker, C. E.

1977-01-01

The program structure is presented. The activities of the thermochemical cycles program are grouped according to the following categories: (1) specific cycle development, (2) support research and technology, (3) cycle evaluation. Specific objectives and status of on-going activities are discussed. Chemical reaction series for the production of hydrogen are presented. Efficiency and economic evaluations are also discussed.

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.

Olivine-modified spinel-spinel transitions in the system Mg2SiO4-Fe2SiO4: Calorimetric measurements, thermochemical calculation, and geophysical application

NASA Astrophysics Data System (ADS)

Akaogi, Masaki; Ito, Eiji; Navrotsky, Alexandra

1989-11-01

The olivine(α)-modified spinel(β)-spinel (γ) transitions in the system Mg2SiO4-Fe2SiO4 were studied by high-temperature solution calorimetry. Enthalpies of the β-γ and a α-γ transitions in Mg2SiO4 at 975 K and of the α-γ transition in Fe2SiO4 at 298 K were measured. The γ solid solution showed a positive enthalpy of mixing. Phase relations at high pressures and high temperatures were calculated from these thermochemical data including correction for the effect of nonideality of α, β, and γ solid solutions. The calculated phase diagrams agree well with those determined experimentally by Katsura and Ito very recently. The α - (Mg0.89, Fe0.11)2SiO4 transforms to β through a region of α+β without passing through the α+γ phase field at around 400 km depth in the mantle with an interval of about 18(±5) km. Temperatures at 390 and 650 km depths are estimated to be about 1673 and 1873 K, respectively, assuming an adiabatic geotherm.

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.

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.

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.

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

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.

Melting and reactive flow of a volatilized mantle beneath mid-ocean ridges: theory and numerical models

NASA Astrophysics Data System (ADS)

Keller, Tobias; Katz, Richard F.

2015-04-01

Laboratory experiments indicate that even small concentrations volatiles (H2O or CO2) in the upper mantle significantly affect the silicate melting behavior [HK96,DH06]. The presence of volatiles stabilizes volatile-rich melt at high pressure, thus vastly increasing the volume of the upper mantle expected to be partially molten [H10,DH10]. These small-degree melts have important consequences for chemical differentiation and could affect the dynamics of mantle flow. We have developed theory and numerical implementation to simulate thermo-chemically coupled magma/mantle dynamics in terms of a two-phase (rock+melt), three component (dunite+MORB+volatilized MORB) physical model. The fluid dynamics is based on McKenzie's equations [McK84], while the thermo-chemical formulation of the system is represented by a novel disequilibrium multi-component melting model based on thermo-dynamic theory [RBS11]. This physical model is implemented as a parallel, two-dimensional, finite-volume code that leverages tools from the PETSc toolkit. Application of this simulation code to a mid-ocean ridge system suggests that the methodology captures the leading-order features of both hydrated and carbonated mantle melting, including deep, low-degree, volatile-rich melt formation. Melt segregation leads to continuous dynamic thermo-chemical dis-equilibration, while phenomenological reaction rates are applied to continually move the system towards re-equilibration. The simulations will be used first to characterize volatile extraction from the MOR system assuming a chemically homogeneous mantle. Subsequently, simulations will be extended to investigate the consequences of heterogeneity in lithology [KW12] and volatile content. These studies will advance our understanding of the role of volatiles in the dynamic and chemical evolution of the upper mantle. Moreover, they will help to gauge the significance of the coupling between the deep carbon cycle and the ocean/atmosphere system. REFERENCES HK96 Hirth & Kohlstedt (1996), Earth Planet Sci Lett DH06 Dasgupta & Hirschmann (2006), doi:10.1038/nature04612. H10 Hirschmann (2010), doi:10.1016/j.pepi.2009.12.003. DH10 Dasgupta & Hirschmann (2010), doi:10.1016/j.epsl.2010.06.039. McK84 McKenzie (1984), J Pet KW12 Katz & Weatherley (2012), doi: 10.1016/j.epsl.2012.04.042. RBS11 Rudge, Bercovici & Spiegelman (2011), doi: 10.1111/j.1365-246X.2010.04870.x

The exploration of exoplanets: What can we learn from solar system synergies?

NASA Astrophysics Data System (ADS)

Encrenaz, Therese

2015-07-01

Most of the discovered exoplanets are "exotic" with regard to the Solar system, with characteristics that are very different from our own planets. Still, we can use the experience gained in the study of the solar system planets for trying to understand the physical nature of exoplanets. The properties of their atmospheres are, as in the case of the Solar system, constrained by a few parameters: their mass and radius, the stellar radiation flux (and thus the star's properties and its distance to the planet), the planet's ellipticity, its inclination, its rotation, the presence or absence of a magnetosphere... Under some simple hypotheses (thermochemical equilibrium and absence of migration), it is possible to make simple predictions about the nature of the exoplanet's atmospheric composition, on the basis of the planet's mass and its equilibrium temperature. The study of solar system planets also tells us which other mechanisms may lead to a departure from thermochemical equilibrium, in particular photochemistry and transport-induced quenching. The study of planetary spectra is a good starting point to try to understand the spectra of exoplanets that now become available through transit spectroscopy observations. From the spectral type of the hosting star and its distance to the exoplanet, one can estimate the spectral ranges where reflected/scattered stellar radiation and thermal emission dominate. In the thermal regime, the observation of a given molecule in different bands of different intensities may provide constraints on the vertical thermal profile and the vertical distribution of the molecule.

Process of producing liquid hydrocarbon fuels from biomass

DOEpatents

Kuester, J.L.

1987-07-07

A continuous thermochemical indirect liquefaction process is described to convert various biomass materials into diesel-type transportation fuels which fuels are compatible with current engine designs and distribution systems comprising feeding said biomass into a circulating solid fluidized bed gasification system to produce a synthesis gas containing olefins, hydrogen and carbon monoxide and thereafter introducing the synthesis gas into a catalytic liquefaction system to convert the synthesis gas into liquid hydrocarbon fuel consisting essentially of C[sub 7]-C[sub 17] paraffinic hydrocarbons having cetane indices of 50+. 1 fig.

Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

PubMed

Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

2017-01-01

Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH 4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH 4 /gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH 4 production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Equilibrium model analysis of waste plastics gasification using CO2 and steam.

PubMed

Kannan, P; Lakshmanan, G; Al Shoaibi, A; Srinivasakannan, C

2017-12-01

Utilization of carbon dioxide (CO 2 ) in thermochemical treatment of waste plastics may significantly help to improve CO 2 recycling, thus simultaneously curtailing dioxins/furans and CO 2 emissions. Although CO 2 is not such an effective gasifying agent as steam, a few investigations have explored the utilization of CO 2 in conjunction with steam to achieve somewhat higher carbon conversion. This work presents a comparative evaluation study of CO 2 and steam gasification of a typical post-consumer waste plastics mixture using an Aspen Plus equilibrium model. The effect of flow rate of gasifying medium (CO 2 and/or steam) and gasification temperature on product gas composition, carbon conversion, and cold gas efficiency has been analyzed. Simulation results demonstrate that CO 2 can serve as a potential gasifying agent for waste plastics gasification. The resulting product gas was rich in CO whereas CO 2 -steam blends yield a wider H 2 /CO ratio, thus extending the applications of the product gas.

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.

Residual Gas in Closed Systems. III: Development and Reduction of Gases Generated by Source Materials

NASA Technical Reports Server (NTRS)

Palosz, W.

2003-01-01

The amounts and composition of residual gases formed in sealed ampoules loaded with different sources (elements and II-VI and IV-VI compounds) after consecutive annealings were investigated. A given source was subjected to a series of heat treatments, with intermediate measurements and removal of the gas accumulated in the system. The results of these experiments are discussed in terms of the underlying thermochemical and kinetic phenomena and practical limitations of reducing the amount of residual gases in sealed ampoules.

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.

Linear actuation using milligram quantities of CL-20 and TAGDNAT.

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

Snedigar, Shane; Salton, Jonathan Robert; Tappan, Alexander Smith

2009-07-01

There are numerous applications for small-scale actuation utilizing pyrotechnics and explosives. In certain applications, especially when multiple actuation strokes are needed, or actuator reuse is required, it is desirable to have all gaseous combustion products with no condensed residue in the actuator cylinder. Toward this goal, we have performed experiments on utilizing milligram quantities of high explosives to drive a millimeter-diameter actuator with a stroke of 30 mm. Calculations were performed to select proper material quantities to provide 0.5 J of actuation energy. This was performed utilizing the thermochemical code Cheetah to calculate the impetus for numerous propellants and tomore » select quantities based on estimated efficiencies of these propellants at small scales. Milligram quantities of propellants were loaded into a small-scale actuator and ignited with an ignition increment and hot wire ignition. Actuator combustion chamber pressure was monitored with a pressure transducer and actuator stroke was monitored using a laser displacement meter. Total actuation energy was determined by calculating the kinetic energy of reaction mass motion against gravity. Of the materials utilized, the best performance was obtained with a mixture of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and bis-triaminoguanidinium(3,3{prime}dinitroazotriazolate) (TAGDNAT).« less

Li-SF(6) Combustion in Stored Chemical Energy Propulsion Systems

DTIC Science & Technology

1990-07-01

S 3. STRUCTURE OF SF6 3ETS IN MOLTEN LI ........... ................. 8 3.1 Mathematical Model ...ill - ABSTRACT Appropriate thermodynamic models and thermo-chemical data for multicompo- nents and immiscible phases have been Incorporated into a code...by a simplified integral model which was improved9 by the use of the local homogeneous flow approximation, equilibrium combustion model and Kc-C-g

Ignition Behavior of alpha-AlH3

DTIC Science & Technology

2010-01-01

nitromethane (Weiser et al., 2007) and Ammonium Perchlorate= HTPB propellants (Deluca et al., 2007) compared to similarly aluminized versions may...aluminum burning times. Combustion, Explosives , and Shockwaves, 41, 533–546. Benson, S.W. 1976. Thermochemical Kinetics, 2nd ed., Wiley Interscience, New...flat-flame burner. 16th International Colloquium on the Dynamic Explosions and Reactive Systems, Krakow, Poland. Brzustowski, T.A., and Glassman, I. 1964

Spontaneous combustion of hydrogen

NASA Technical Reports Server (NTRS)

Nusselt, Wilhelm; Pothmann, PH

1923-01-01

It is shown by the author's experiments that hydrogen which escapes to the atmosphere through openings in the system may burn spontaneously if it contains dust. Purely thermal reasoning can not account for the combustion. It seems to be rather an electrical ignition. In order to determine whether the cause of the spontaneous ignition was thermo-chemical, thermo-mechanical, or thermo-electrical, the experiments in this paper were performed.

Semiempirical evaluation of post-Hartree-Fock diagonal-Born-Oppenheimer corrections for organic molecules.

PubMed

Mohallem, José R

2008-04-14

Recent post-Hartree-Fock calculations of the diagonal-Born-Oppenheimer correction empirically show that it behaves quite similar to atomic nuclear mass corrections. An almost constant contribution per electron is identified, which converges with system size for specific series of organic molecules. This feature permits pocket-calculator evaluation of the corrections within thermochemical accuracy (10(-1) mhartree or kcal/mol).

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.

Thermochemical tests on resins: Char resistance of selected phenolic cured epoxides

NASA Technical Reports Server (NTRS)

Keck, F. L.

1982-01-01

Curing epoxy resins with novalac phenolic resins is a feasible approach for increasing intact char of the resin system. Char yields above 40% at 700 C were achieved with epoxy novalac (DEN 438)/novalac phenolic (BRWE 5833) resin systems with or without catalyst such as ethyl tri-phenyl phosphonium iodide. These char yields are comparable to commercially used epoxy resin systems like MY-720/DDS/BF3. Stable prepregs are easily made from a solvent solution of the epoxy/phenolic system and this provides a feasible process for fabrication of same into commercial laminates.

Thermochemical generation of hydrogen and carbon dioxide

NASA Technical Reports Server (NTRS)

Lawson, Daniel D. (Inventor); England, Christopher (Inventor)

1984-01-01

Mixing of carbon in the form of high sulfur coal with sulfuric acid reduces the temperature of sulfuric acid decomposition from 830.degree. C. to between 300.degree. C. and 400.degree. C. The low temperature sulfuric acid decomposition is particularly useful in thermal chemical cycles for splitting water to produce hydrogen. Carbon dioxide is produced as a commercially desirable byproduct. Lowering of the temperature for the sulfuric acid decomposition or oxygen release step simplifies equipment requirements, lowers thermal energy input and reduces corrosion problems presented by sulfuric acid at conventional cracking temperatures. Use of high sulfur coal as the source of carbon for the sulfuric acid decomposition provides an environmentally safe and energy efficient utilization of this normally polluting fuel.

Catalytic cartridge SO.sub.3 decomposer

DOEpatents

Galloway, Terry R.

1982-01-01

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO.sub.3 decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO.sub.3 gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO.sub.3 gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety.

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.

Biomass-derived Syngas Utilization for Fuels and Chemicals - Final Report

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

Dayton, David C

2010-03-24

Executive Summary The growing gap between petroleum production and demand, mounting environmental concerns, and increasing fuel prices have stimulated intense interest in research and development (R&D) of alternative fuels, both synthetic and bio-derived. Currently, the most technically defined thermochemical route for producing alternative fuels from lignocellulosic biomass involves gasification/reforming of biomass to produce syngas (carbon monoxide [CO] + hydrogen [H2]), followed by syngas cleaning, Fischer-Tropsch synthesis (FTS) or mixed alcohol synthesis, and some product upgrading via hydroprocessing or separation. A detailed techno-economic analysis of this type of process has recently been published [1] and it highlights the need for technicalmore » breakthroughs and technology demonstration for gas cleanup and fuel synthesis. The latter two technical barrier areas contribute 40% of the total thermochemical ethanol cost and 70% of the production cost, if feedstock costs are factored out. Developing and validating technologies that reduce the capital and operating costs of these unit operations will greatly reduce the risk for commercializing integrated biomass gasification/fuel synthesis processes for biofuel production. The objective of this project is to develop and demonstrate new catalysts and catalytic processes that can efficiently convert biomass-derived syngas into diesel fuel and C2-C4 alcohols. The goal is to improve the economics of the processes by improving the catalytic activity and product selectivity, which could lead to commercialization. The project was divided into 4 tasks: Task 1: Reactor Systems: Construction of three reactor systems was a project milestone. Construction of a fixed-bed microreactor (FBR), a continuous stirred tank reactor (CSTR), and a slurry bubble column reactor (SBCR) were completed to meet this milestone. Task 2: Iron Fischer-Tropsch (FT) Catalyst: An attrition resistant iron FT catalyst will be developed and tested. Task 3: Chemical Synthesis: Promising process routes will be identified for synthesis of selected chemicals from biomass-derived syngas. A project milestone was to select promising mixed alcohol catalysts and screen productivity and performance in a fixed bed micro-reactor using bottled syngas. This milestone was successfully completed in collaboration withour catalyst development partner. Task 4: Modeling, Engineering Evaluation, and Commercial Assessment: Mass and energy balances of conceptual commercial embodiment for FT and chemical synthesis were completed.« less

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

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

Waste biomass-to-energy supply chain management: a critical synthesis.

PubMed

Iakovou, E; Karagiannidis, A; Vlachos, D; Toka, A; Malamakis, A

2010-10-01

The development of renewable energy sources has clearly emerged as a promising policy towards enhancing the fragile global energy system with its limited fossil fuel resources, as well as for reducing the related environmental problems. In this context, waste biomass utilization has emerged as a viable alternative for energy production, encompassing a wide range of potential thermochemical, physicochemical and bio-chemical processes. Two significant bottlenecks that hinder the increased biomass utilization for energy production are the cost and complexity of its logistics operations. In this manuscript, we present a critical synthesis of the relative state-of-the-art literature as this applies to all stakeholders involved in the design and management of waste biomass supply chains (WBSCs). We begin by presenting the generic system components and then the unique characteristics of WBSCs that differentiate them from traditional supply chains. We proceed by discussing state-of-the-art energy conversion technologies along with the resulting classification of all relevant literature. We then recognize the natural hierarchy of the decision-making process for the design and planning of WBSCs and provide a taxonomy of all research efforts as these are mapped on the relevant strategic, tactical and operational levels of the hierarchy. Our critical synthesis demonstrates that biomass-to-energy production is a rapidly evolving research field focusing mainly on biomass-to-energy production technologies. However, very few studies address the critical supply chain management issues, and the ones that do that, focus mainly on (i) the assessment of the potential biomass and (ii) the allocation of biomass collection sites and energy production facilities. Our analysis further allows for the identification of gaps and overlaps in the existing literature, as well as of critical future research areas. (c) 2010 Elsevier Ltd. All rights reserved.

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.

Nonequilibrium thermo-chemical calculations using a diagonal implicit scheme

NASA Technical Reports Server (NTRS)

Imlay, Scott T.; Roberts, Donald W.; Soetrisno, Moeljo; Eberhardt, Scott

1991-01-01

A recently developed computer program for hypersonic vehicle flow analysis is described. The program uses a diagonal implicit algorithm to solve the equations of viscous flow for a gas in thermochemical nonequilibrium. The diagonal scheme eliminates the expense of inverting large block matrices that arise when species conservation equations are introduced. The program uses multiple zones of grids patched together and includes radiation wall and rarefied gas boundary conditions. Solutions are presented for hypersonic flows of air and hydrogen air mixtures.

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.

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.

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.

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.

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.

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.

Different mechanisms of magnetisation recorded in experimental fires: Archaeomagnetic implications

NASA Astrophysics Data System (ADS)

Carrancho, Á.; Villalaín, J. J.

2011-12-01

We present here the archaeomagnetic and rock-magnetic results obtained from the experimental recreation of prehistoric fires on a clayish soil substratum. By using a system of thermocouples that allows the control of temperatures and heat penetration with depth, the magneto-mineralogical transformations as well as the ability to acquire magnetic remanences are studied. A detailed set of rock-magnetic analyses - carried out both on surface and depth with a millimetre scale resolution- shows the creation of post-burn magnetite over the entire surface of the hearth, thus promoting a distinguishable magnetic enhancement. On the basis of a detailed control of temperatures, interesting differences between areas (centre vs. periphery) were observed and two different mechanisms of magnetisation have been recorded. The central area which exceeded 600 °C acquired a thermal remanent magnetisation (TRM) and the periphery, which was heated up to 300 °C, recorded a thermo-chemical (TCRM) remanent magnetisation. The most noticeable mineralogical changes are focused to the first centimetre of the central area, where single-domain magnetite has been created. The implications of these results for archaeomagnetic and palaeointensity studies as well as their utility for the detection of fire in archaeological sites are discussed.

Additional and revised thermochemical data and computer code for WATEQ2: a computerized chemical model for trace and major element speciation and mineral equilibria of natural waters

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Jenne, Everett A.

1980-01-01

A computerized chemical model, WATEQ2, has resulted from extensive additions to and revision of the WATEQ model of Truesdell and Jones (Truesdell, A. H., and Jones, B. F., 1974, WATEQ, a computer program for calculating chemical equilibria of natural waters: J. Res. U. S. Geol, Survey, v. 2, p. 233-274). The model building effort has necessitated searching the literature and selecting thermochemical data pertinent to the reactions added to the model. This supplementary report manes available the details of the reactions added to the model together with the selected thermochemical data and their sources. Also listed are details of program operation and a brief description of the output of the model. Appendices-contain a glossary of identifiers used in the PL/1 computer code, the complete PL/1 listing, and sample output from three water analyses used as test cases.

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.

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

Current evaluation of the tripropellant concept

NASA Technical Reports Server (NTRS)

Zurawski, R. L.

1986-01-01

An analytical study was conducted to determine the specific-impulse advantages of adding metals to conventional liquid-bipropellant systems. These tripropellant systems theoretically offer higher specific impulse and increased propellant density compared with bipropellant systems. Metals considered were Be, Li, and Al. Bipropellant systems were H2/O2, N2H4/N2O4, RP-1/O2, and H2/F2. Thermochemical calculations were performed for sea-level expansion from 6.895-MN/sq. m. (1000-psia) chamber pressure over a wide range of mixture ratios and propellant compositions. Three-dimensional plots characterize the specific impulse of each tripropellant system. Technology issues pertinent to metallized propellant systems are discussed.

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

Catalytic cartridge SO/sub 3/ decomposer

DOEpatents

Galloway, T.R.

1980-11-18

A catalytic cartridge surrounding a heat pipe driven by a heat source is utilized as a SO/sub 3/ decomposer for thermochemical hydrogen production. The cartridge has two embodiments, a cross-flow cartridge and an axial flow cartridge. In the cross-flow cartridge, SO/sub 3/ gas is flowed through a chamber and incident normally to a catalyst coated tube extending through the chamber, the catalyst coated tube surrounding the heat pipe. In the axial-flow cartridge, SO/sub 3/ gas is flowed through the annular space between concentric inner and outer cylindrical walls, the inner cylindrical wall being coated by a catalyst and surrounding the heat pipe. The modular cartridge decomposer provides high thermal efficiency, high conversion efficiency, and increased safety. A fusion reactor may be used as the heat source.

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

Thermochemical Wastewater Valorization via Enhanced Microbial Toxicity Tolerance

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

Beckham, Gregg T; Thelhawadigedara, Lahiru Niroshan Jayakody; Johnson, Christopher W

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

HCN production from impact ejecta on the early Earth

NASA Astrophysics Data System (ADS)

Parkos, Devon; Pikus, Aaron; Alexeenko, Alina; Melosh, H. J.

2016-11-01

Major impact events have drastically altered the evolution of life on Earth. The reentry of ejecta formed from these events can trigger widespread chemical changes to the atmosphere on a global scale. This mechanism was proposed as a source of HCN during the Late Heavy Bombardment (LHB), 4.1 to 3.8 billion years ago. Significant concentrations of HCN in surface water could directly lead to adenine formation, a precursor for RNA. This work uses the Direct Simulation Monte Carlo (DSMC) method to examine the production of CN and HCN due to the reentry of impact ejecta. We use the Statistical Modeling in Low-Density Environment (SMILE) code, which utilizes the Total Collisional Energy (TCE) model for reactions. The collisions are described by the Variable Soft Sphere (VSS) and Larsen-Borgnakke (LB) models. We compare this nonequilibrium production to equilibrium concentrations from bulk atmospheric heating. The equilibrium HCN yield for a 1023 J impact is 7.0×104 moles, corresponding to a 2.5×1014 molecules per m2 surface deposition. We find that additional CN and HCN is produced under thermochemical nonequilibrium, particularly at higher altitudes. The total nonequilibrium yield for a 1023 J impact is 1.2×106 moles of HCN, a value 17 times the equilibrium result. This corresponds to a surface deposition of 1.4×1015 molecules per m2. This increase in production indicates that thermochemical nonequilibrium effects play a strong role in HCN from impact ejecta, and must be considered when investigating impacts as a plausible mechanism for significant adenine production during the LHB.

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

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O2 + 4e– + 4H+ ⇌ 2H2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc+/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the free energy for transferring water frommore » aqueous solution to organic solvent, -0.43 kcal mol–1 for MeCN and -1.47 kcal mol–1 for DMF, and the potential of the H+/H2 couple, – 0.028 V in MeCN and -0.662 V in DMF. The H+/H2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O2/H2O couple has been extended to the CO2/CO and CO2/CH4 couples to give values of -0.12 and +0.15 V in MeCN and -0.73 and -0.48 V in DMF, respectively. Extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol–1 for acetonitrile and +0.6 kcal mol–1 for DMF.« less

An evaluation of negative-emission transportation-energy systems for the US

NASA Astrophysics Data System (ADS)

Larson, E. D.; Meerman, J. C.

2017-12-01

We present technical, economic, and carbon footprint evaluations of alternative technological pathways for negative emissions transportation energy from sustainably-sourced lignocellulosic biomass in the U.S. We combine the understanding of alternative technological pathways with spatially-resolved projections of the sustainable supply of lignocellulosic biomass and with future demands for transportation services to provide insights on the extent to which biomass-based energy might be able to help meet mid-century U.S. transportation energy needs and carbon mitigation targets. Biomass conversion routes included in our evaluations are biochemical, biocatalytic, thermocatalytic hydropyrolysis, and thermochemical gasification/synthesis to produce liquid fuels fungible with petroleum-derived fuels, and thermochemical conversion to hydrogen (for fuel cell vehicles) or electricity (for battery electric vehicles). Lifecycle net negative emissions are achieved for each system via soil carbon buildup during biomass production and/or capture of CO2 at the conversion facility and underground storage. Co-processing of some fossil fuel is considered in some cases to improve economics. For self-consistency in the analysis across systems, a common set of technical, economic and carbon footprint input parameters are adopted. Capital cost estimates are harmonized by taking into account scale of facilities, level of engineering details available in generating a cost estimate, and the technology readiness level (TRL) of components and the process as a whole. Implications for economics of future commercial plants are investigated, considering alternative prospective reductions in capital and operating costs (via "learning by doing") and alternative carbon mitigation policies.

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

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.

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.

Life cycle assessment of nuclear-based hydrogen production via thermochemical water splitting using a copper-chlorine (Cu-Cl) cycle

NASA Astrophysics Data System (ADS)

Ozbilen, Ahmet Ziyaettin

The energy carrier hydrogen is expected to solve some energy challenges. Since its oxidation does not emit greenhouse gases (GHGs), its use does not contribute to climate change, provided that it is derived from clean energy sources. Thermochemical water splitting using a Cu-Cl cycle, linked with a nuclear super-critical water cooled reactor (SCWR), which is being considered as a Generation IV nuclear reactor, is a promising option for hydrogen production. In this thesis, a comparative environmental study is reported of the three-, four- and five-step Cu-Cl thermochemical water splitting cycles with various other hydrogen production methods. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step Cu-Cl cycles due to its lower thermal energy requirement. Parametric studies show that acidification potentials (APs) and global warming potentials (GWPs) for the four-step Cu-Cl cycle can be reduced from 0.0031 to 0.0028 kg SO2-eq and from 0.63 to 0.55 kg CO2-eq, respectively, if the lifetime of the system increases from 10 to 100 years. Moreover, the comparative study shows that the nuclear-based S-I and the four-step Cu-Cl cycles are the most environmentally benign hydrogen production methods in terms of AP and GWP. GWPs of the S-I and the four-step Cu-Cl cycles are 0.412 and 0.559 kg CO2-eq for reference case which has a lifetime of 60 years. Also, the corresponding APs of these cycles are 0.00241 and 0.00284 kg SO2-eq. It is also found that an increase in hydrogen plant efficiency from 0.36 to 0.65 decreases the GWP from 0.902 to 0.412 kg CO 2-eq and the AP from 0.00459 to 0.00209 kg SO2-eq for the four-step Cu-Cl cycle. Keywords: Hydrogen production, nuclear energy, Cu-Cl cycle, environmental impact, LCA.

New developments in theoretical thermochemistry and electronic structure applications in supramolecular chemistry and cluster science

NASA Astrophysics Data System (ADS)

Ramabhadran, Raghunath Ozhapakkam

In a concise display of the power and diversity of electronic structure theory (EST), the work presented herein involves the development of new computational methods to advance the practical utility of quantum chemistry, as well as solving different types of challenging chemical problems by applying existing EST tools. The research presented is highly interdisciplinary in nature and features synergistic collaborations to solve real-life problems such as regulating toxic chemicals and generating alternative sources of energy. In the first chapter of this dissertation, the solution to a long-standing problem in theoretical thermochemistry is accomplished by the development of the automated, chemically intuitive and generalized thermochemical hierarchy, Connectivity-Based Hierarchy (CBH) to accurately predict the thermochemical properties of organic molecules. The extension of the hierarchy to predict the enthalpies of formations of biomonomers such as amino acids is also presented. The development of a computationally efficient protocol to accurately extrapolate to high CCSD(T) energies based on MP2 and DFT energies using CBH is presented in the second chapter, thus merging theoretical thermochemistry with fragment-based methods in quantum chemistry. This merger drastically reduces the computational cost involved in a CCSD(T) calculation, while retaining the impeccable accuracy it offers. The practical utility of the CH hydrogen bond, commonly thought as being too weak to be used in supramolecular applications has been demonstrated by DFT calculations (along with experimental results from the Flood group) in the third chapter. This is accomplished by systematically studying the binding of monoatomic chloride, diatomic and toxic cyanide and the polyatomic bi-fluoride anions for the first time using only CH hydrogen bonds within a triazolophane macrocycle. The fourth chapter contains the introduction of the concept of fluxionality in the chemical reactions of transition metal oxide clusters. This is useful to develop a systematic paradigm for discussing the mechanisms in the reactions of larger transition metal oxide clusters with small molecules. Additionally, DFT calculations (along with experimental results from the C. C. Jarrold group) are shown to be useful to provide new insights on hydrogen liberation from water, thus aiding in the generation of alternative sources of energy.

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 Detailed, Finite-Rate, Chemical Kinetics Mechanism for Monomethylhydrazine-Red Fuming Nitric Acid Systems

DTIC Science & Technology

2010-02-01

nitromethane . When the effort to develop the MMH-RFNA mechanism was discontinued in 2005, the mechanism was composed of rate expressions and...results comparable to those predicted by the theory of thermal explosions . Thermochemical parameters for molecules unique to these two mechanisms were...Bendtsen, A. B.; Miller, J. A. Nitromethane Dissociation: Implications for the CH3 + NO2 Reaction. Int. J. Chemical Kinetics 1999, 31, 591–602. Kee, R

Investigation of thermochemical biorefinery sizing and environmental sustainability impacts for conventional supply system and distributed pre-processing supply system designs

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

David J. Muth, Jr.; Matthew H. Langholtz; Eric C. D. Tan

The 2011 US Billion-Ton Update estimates that by 2030 there will be enough agricultural and forest resources to sustainably provide at least one billion dry tons of biomass annually, enough to displace approximately 30% of the country's current petroleum consumption. A portion of these resources are inaccessible at current cost targets with conventional feedstock supply systems because of their remoteness or low yields. Reliable analyses and projections of US biofuels production depend on assumptions about the supply system and biorefinery capacity, which, in turn, depend upon economic value, feedstock logistics, and sustainability. A cross-functional team has examined combinations of advancesmore » in feedstock supply systems and biorefinery capacities with rigorous design information, improved crop yield and agronomic practices, and improved estimates of sustainable biomass availability. A previous report on biochemical refinery capacity noted that under advanced feedstock logistic supply systems that include depots and pre-processing operations there are cost advantages that support larger biorefineries up to 10 000 DMT/day facilities compared to the smaller 2000 DMT/day facilities. This report focuses on analyzing conventional versus advanced depot biomass supply systems for a thermochemical conversion and refinery sizing based on woody biomass. The results of this analysis demonstrate that the economies of scale enabled by advanced logistics offsets much of the added logistics costs from additional depot processing and transportation, resulting in a small overall increase to the minimum ethanol selling price compared to the conventional logistic supply system. While the overall costs do increase slightly for the advanced logistic supply systems, the ability to mitigate moisture and ash in the system will improve the storage and conversion processes. In addition, being able to draw on feedstocks from further distances will decrease the risk of biomass supply to the conversion facility.« less

Investigation of thermochemical biorefinery sizing and environmental sustainability impacts for conventional supply system and distributed preprocessing supply system designs

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

Muth, jr., David J.; Langholtz, Matthew H.; Tan, Eric

2014-03-31

The 2011 US Billion-Ton Update estimates that by 2030 there will be enough agricultural and forest resources to sustainably provide at least one billion dry tons of biomass annually, enough to displace approximately 30% of the country's current petroleum consumption. A portion of these resources are inaccessible at current cost targets with conventional feedstock supply systems because of their remoteness or low yields. Reliable analyses and projections of US biofuels production depend on assumptions about the supply system and biorefinery capacity, which, in turn, depend upon economic value, feedstock logistics, and sustainability. A cross-functional team has examined combinations of advancesmore » in feedstock supply systems and biorefinery capacities with rigorous design information, improved crop yield and agronomic practices, and improved estimates of sustainable biomass availability. A previous report on biochemical refinery capacity noted that under advanced feedstock logistic supply systems that include depots and pre-processing operations there are cost advantages that support larger biorefineries up to 10 000 DMT/day facilities compared to the smaller 2000 DMT/day facilities. This report focuses on analyzing conventional versus advanced depot biomass supply systems for a thermochemical conversion and refinery sizing based on woody biomass. The results of this analysis demonstrate that the economies of scale enabled by advanced logistics offsets much of the added logistics costs from additional depot processing and transportation, resulting in a small overall increase to the minimum ethanol selling price compared to the conventional logistic supply system. While the overall costs do increase slightly for the advanced logistic supply systems, the ability to mitigate moisture and ash in the system will improve the storage and conversion processes. In addition, being able to draw on feedstocks from further distances will decrease the risk of biomass supply to the conversion facility.« less

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.

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.

High-temperature molten salt solar thermal systems

NASA Astrophysics Data System (ADS)

Copeland, R. J.; Leach, J. W.; Stern, G.

Conceptual designs of a solar thermal central receiver and a thermal storage subsystem were analyzed to estimate thermal losses and to assess the economics of high-temperature applications with molten salt transport fluids. Modifications to a receiver design being developed by the Martin Marietta Corporation were studied to investigate possible means for improving efficiency at high temperatures. Computations were made based on conceptual design of internally insulated high temperature storage tanks to estimate cost and performance. A study of a potential application of the system for thermochemical production of hydrogen indicates that thermal storage at 1100 C will be economically attractive.

A Thermochemical Kinetic-Based Study of Ignition Delays for 2-Azidoethanamine-Red Fuming Nitric Acid Systems: 2-Azido-N-Methylethanamine (MMAZ) Vs. 2-Azido-N,N-Dimethylethanamine (DMAZ)

DTIC Science & Technology

2014-01-01

ABSTRACT UU 18. NUMBER OF PAGES 68 19a. NAME OF RESPONSIBLE PERSON Chiung-Chu Chen a. REPORT Unclassified b. ABSTRACT Unclassified c ...Abstraction Reactions 33 Appendix C . Geometric Representations, Normal Mode Frequencies, and Moments of Inertia for Molecular Structures Involved in...from MMAZ and DMAZ by NO2 are also shown. ....................13 Figure 6. Potential energy diagram for the C •H2NHCH2CH2N3 + NO2 system: G4-based

Computer-Based Methods for Thermodynamic Analysis of Materials Processing.

DTIC Science & Technology

1983-11-30

metallic alloys (12,13), silicides (14),and oxynitride * . systems (15). - . 2. Thermochemical System Employed to Characterize Binary Ill-V Phase Diagrams The...reference to Figure I shows that the stable form of RbF is the sodium chloride S form. Table I shows that OGH -oS -RFRFLS-RFRFLM-12866-.381T J/g.at. (5...KF, BF=(I/3)8aF LF-(I/4)LaF3V PF-(113)PbF 2 S- Sodium Chloride Structures Stable form of NF, KE, RE and (;F L-Liquid, M-Stable form of ZF, KeStable form

Biomass conversion processes for energy and fuels

NASA Astrophysics Data System (ADS)

Sofer, S. S.; Zaborsky, O. R.

The book treats biomass sources, promising processes for the conversion of biomass into energy and fuels, and the technical and economic considerations in biomass conversion. Sources of biomass examined include crop residues and municipal, animal and industrial wastes, agricultural and forestry residues, aquatic biomass, marine biomass and silvicultural energy farms. Processes for biomass energy and fuel conversion by direct combustion (the Andco-Torrax system), thermochemical conversion (flash pyrolysis, carboxylolysis, pyrolysis, Purox process, gasification and syngas recycling) and biochemical conversion (anaerobic digestion, methanogenesis and ethanol fermentation) are discussed, and mass and energy balances are presented for each system.

Symmetrization of conservation laws with entropy for high-temperature hypersonic computations

NASA Technical Reports Server (NTRS)

Chalot, F.; Hughes, T. J. R.; Shakib, F.

1990-01-01

Results of Hughes, France, and Mallet are generalized to conservation law systems taking into account high-temperature effects. Symmetric forms of different equation sets are derived in terms of entropy variables. First, the case of a general divariant gas is studied; it can be specialized to the usual Navier-Stokes equations, as well as to situations where the gas is vibrationally excited, and undergoes equilibrium chemical reactions. The case of gas in thermochemical nonequilibrium is considered next. Transport phenomena, and in particular mass diffusion, are examined in the framework of symmetric advective-diffusive systems.

Surface Catalysis and Characterization of Proposed Candidate TPS for Access-to-Space Vehicles

NASA Technical Reports Server (NTRS)

Stewart, David A.

1997-01-01

Surface properties have been obtained on several classes of thermal protection systems (TPS) using data from both side-arm-reactor and arc-jet facilities. Thermochemical stability, optical properties, and coefficients for atom recombination were determined for candidate TPS proposed for single-stage-to-orbit vehicles. The systems included rigid fibrous insulations, blankets, reinforced carbon carbon, and metals. Test techniques, theories used to define arc-jet and side-arm-reactor flow, and material surface properties are described. Total hemispherical emittance and atom recombination coefficients for each candidate TPS are summarized in the form of polynomial and Arrhenius expressions.

Millimeter-wave spectra of the Jovian planets

NASA Technical Reports Server (NTRS)

Joiner, Joanna; Steffes, Paul G.

1991-01-01

The millimeter wave portion of the electromagnetic spectrum is critical for understanding the subcloud atmospheric structure of the Jovian planets (Jupiter, Saturn, Uranus, and Neptune). This research utilizes a combination of laboratory measurements, computer modeling, and radio astronomical observation in order to obtain a better understanding of the millimeter-wave spectra of the Jovian planets. The pressure broadened absorption from gaseous ammonia (NH3) and hydrogen sulfide (H2S) was measured in the laboratory under simulated conditions for the Jovian atmospheres. Researchers developed new formalisms for computing the absorptivity of gaseous NH3 and H2S based on their laboratory measurements. They developed a radiative transfer and thermochemical model to predict the abundance and distribution of absorbing constituents in the Jovian atmospheres. They used the model to compute the millimeter wave emission from the Jovian planets.

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.

Water circulation and global mantle dynamics: Insight from numerical modeling

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi; Nakakuki, Tomoeki; Iwamori, Hikaru

2015-05-01

We investigate water circulation and its dynamical effects on global-scale mantle dynamics in numerical thermochemical mantle convection simulations. Both dehydration-hydration processes and dehydration melting are included. We also assume the rheological properties of hydrous minerals and density reduction caused by hydrous minerals. Heat transfer due to mantle convection seems to be enhanced more effectively than water cycling in the mantle convection system when reasonable water dependence of viscosity is assumed, due to effective slab dehydration at shallow depths. Water still affects significantly the global dynamics by weakening the near-surface oceanic crust and lithosphere, enhancing the activity of surface plate motion compared to dry mantle case. As a result, including hydrous minerals, the more viscous mantle is expected with several orders of magnitude compared to the dry mantle. The average water content in the whole mantle is regulated by the dehydration-hydration process. The large-scale thermochemical anomalies, as is observed in the deep mantle, is found when a large density contrast between basaltic material and ambient mantle is assumed (4-5%), comparable to mineral physics measurements. Through this study, the effects of hydrous minerals in mantle dynamics are very important for interpreting the observational constraints on mantle convection.

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

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

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.

Effects of Impurities and Processing on Silicon Solar Cells, Phase 3

NASA Technical Reports Server (NTRS)

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

1979-01-01

Results of the 14th quarterly report are presented for a program designed to assess the effects of impurities, thermochemical processes and any impurity process interactions on the performance of terrestrial silicon solar cells. The Phase 3 effort encompasses: (1) potential interactions between impurities and thermochemical processing of silicon; (2) impurity-cell performance relationships in n-base silicon; (3) effect of contaminants introduced during silicon production, refining or crystal growth on cell performance; (4) effects of nonuniform impurity distributions in large area silicon wafers; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells.

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.

Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

USGS Publications Warehouse

Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

2013-01-01

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Reliability Estimating Procedures for Electric and Thermochemical Propulsion Systems. Volume 2

DTIC Science & Technology

1977-02-01

final form. For some components, the parameters are calculated from design factors (e.g., design life) that must be input when requested. Each component...Components Components are regarded as statis- tically identical if they are drawn from the same production lot because the initial and sub- sequent...table yields b 0.0023 The - factors are obtained from Tables 2.2.4-1 through 2.2.4-5: Factor Value rE Space, flight 1 JANTXV quality 0.5 7A Small signal

Studies of the use of heat from high temperature nuclear sources for hydrogen production processes

NASA Technical Reports Server (NTRS)

Farbman, G. H.

1976-01-01

Future uses of hydrogen and hydrogen production processes that can meet the demand for hydrogen in the coming decades were considered. To do this, a projection was made of the market for hydrogen through the year 2000. Four hydrogen production processes were selected, from among water electrolysis, fossil based and thermochemical water decomposition systems, and evaluated, using a consistent set of ground rules, in terms of relative performance, economics, resource requirements, and technology status.

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

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

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Thermochemical valorization and characterization of household biowaste.

PubMed

Vakalis, S; Sotiropoulos, A; Moustakas, K; Malamis, D; Vekkos, K; Baratieri, M

2017-12-01

Valorization of municipal solid waste (MSW), by means of energy and material recovery, is considered to be a crucial step for sustainable waste management. A significant fraction of MSW is comprised from food waste, the treatment of which is still a challenge. Therefore, the conventional disposal of food waste in landfills is being gradually replaced by recycling aerobic treatment, anaerobic digestion and waste-to-energy. In principle, thermal processes like combustion and gasification are preferred for the recovery of energy due to the higher electrical efficiency and the significantly less time required for the process to be completed when compared to biological process, i.e. composting, anaerobic digestion and transesterification. Nonetheless, the high water content and the molecular structure of biowaste are constraining factors in regard to the application of thermal conversion pathways. Investigating alternative solutions for the pre-treatment and more energy efficient handling of this waste fraction may provide pathways for the optimization of the whole process. In this study, by means of utilizing drying/milling as an intermediate step, thermal treatment of household biowaste has become possible. Household biowaste has been thermally processed in a bench scale reactor by means of torrefaction, carbonization and high temperature pyrolysis. According to the operational conditions, fluctuating fractions of biochar, bio-oil (tar) and syngas were recovered. The thermochemical properties of the feedstock and products were analyzed by means of Simultaneous Thermal Analysis (STA), Ultimate and Proximate analysis and Attenuated Total Reflectance (ATR). The analysis of the products shows that torrefaction of dried household biowaste produces an energy dense fuel and high temperature pyrolysis produces a graphite-like material with relatively high yield. Copyright © 2016 Elsevier Ltd. All rights reserved.

Standard reduction potentials for oxygen and carbon dioxide couples in acetonitrile and N, N -dimethylformamide

DOE PAGES

Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J.; ...

2015-12-07

A variety of next-generation energy processes utilize the electrochemical interconversions of dioxygen and water as the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Reported here are the first estimates of the standard reduction potential of the O 2 + 4e – + 4H + ⇌ 2H 2O couple in organic solvents. The values are +1.21 V in acetonitrile (MeCN) and +0.60 V in N,N-dimethylformamide (DMF), each versus the ferrocenium/ferrocene couple (Fc +/0) in the respective solvent (as are all of the potentials reported here). The potentials have been determined using a thermochemical cycle that combines the freemore » energy for transferring water from aqueous solution to organic solvent, –0.43 kcal mol –1 for MeCN and –1.47 kcal mol –1 for DMF, and the potential of the H +/H 2 couple, – 0.028 V in MeCN and –0.662 V in DMF. The H +/H 2 couple in DMF has been directly measured electrochemically using the previously reported procedure for the MeCN value. The thermochemical approach used for the O 2/H 2O couple has been extended to the CO 2/CO and CO 2/CH 4 couples to give values of –0.12 and +0.15 V in MeCN and –0.73 and –0.48 V in DMF, respectively. Here, extensions to other reduction potentials are discussed. Additionally, the free energy for transfer of protons from water to organic solvent is estimated as +14 kcal mol –1 for acetonitrile and +0.6 kcal mol –1 for DMF.« less

Technician's Perspective on an Ever-Changing Research Environment: Catalytic Conversion of Biomass to Fuels

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

Thibodeaux, J.; Hensley, J.

2013-01-01

The biomass thermochemical conversion platform at the National Renewable Energy Laboratory (NREL) develops and demonstrates processes for the conversion of biomass to fuels and chemicals including gasification, pyrolysis, syngas clean-up, and catalytic synthesis of alcohol and hydrocarbon fuels. In this talk, I will discuss the challenges of being a technician in this type of research environment, including handling and working with catalytic materials and hazardous chemicals, building systems without being given all of the necessary specifications, pushing the limits of the systems through ever-changing experiments, and achieving two-way communication with engineers and supervisors. I will do this by way ofmore » two examples from recent research. First, I will describe a unique operate-to-failure experiment in the gasification of chicken litter that resulted in the formation of a solid plug in the gasifier, requiring several technicians to chisel the material out. Second, I will compare and contrast bench scale and pilot scale catalyst research, including instances where both are conducted simultaneously from common upstream equipment. By way of example, I hope to illustrate the importance of researchers 1) understanding the technicians' perspective on tasks, 2) openly communicating among all team members, and 3) knowing when to voice opinions. I believe the examples in this talk will highlight the crucial role of a technical staff: skills attained by years of experience to build and operate research and production systems. The talk will also showcase the responsibilities of NREL technicians and highlight some interesting behind-the-scenes work that makes data generation from NREL's thermochemical process development unit possible.« less

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.

Integrated biomass pyrolysis with organic Rankine cycle for power generation

NASA Astrophysics Data System (ADS)

Nur, T. B.; Syahputra, A. W.

2018-02-01

The growing interest on Organic Rankine Cycle (ORC) application to produce electricity by utilizing biomass energy sources are increasingly due to its successfully used to generate power from waste heat available in industrial processes. Biomass pyrolysis is one of the thermochemical technologies for converting biomass into energy and chemical products consisting of liquid bio-oil, solid biochar, and pyrolytic gas. In the application, biomass pyrolysis can be divided into three main categories; slow, fast and flash pyrolysis mainly aiming at maximizing the products of bio-oil or biochar. The temperature of synthesis gas generated during processes can be used for Organic Rankine Cycle to generate power. The heat from synthesis gas during pyrolysis processes was transfer by thermal oil heater to evaporate ORC working fluid in the evaporator unit. In this study, the potential of the palm oil empty fruit bunch, palm oil shell, and tree bark have been used as fuel from biomass to generate electricity by integrated with ORC. The Syltherm-XLT thermal oil was used as the heat carrier from combustion burner, while R245fa was used as the working fluid for ORC system. Through Aspen Plus, this study analyses the influences on performance of main thermodynamic parameters, showing the possibilities of reaching an optimum performance for different working conditions that are characteristics of different design parameters.

Energy storage for a lunar base by the reversible chemical reaction: CaO+H2O reversible reaction Ca(OH)2

NASA Technical Reports Server (NTRS)

Perez-Davis, Marla E.; Difilipo, Frank

1990-01-01

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. The specific energy (energy to mass ratio) of the system was estimated to be 155 W-hr/kg. 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 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.

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.

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.

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.

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

Udengaard, Niels; Knight, Richard; Wendt, Jesper

This final report presents the results of a four-year technology demonstration project carried out by a consortium of companies sponsored in part by a $25 million funding by the Department of Energy (DOE) under the American Recovery and Reinvestment Act (ARRA). The purpose of the project was to demonstrate a new, economical technology for the thermochemical conversion of woody biomass into gasoline and to demonstrate that the gasoline produced in this way is suitable for direct inclusion in the already existing gasoline pool. The process that was demonstrated uses the Andritz-Carbona fluidized-bed steam-oxygen gasification technology and advanced tar reforming catalyticmore » systems to produce a clean syngas from waste wood, integrated conventional gas cleanup steps, and finally utilizes Haldor Topsoe’s (Topsoe) innovative Topsoe Improved Gasoline Synthesis (TIGASTM) syngas-to-gasoline process. Gas Technology Institute (GTI) carried out the bulk of the testing work at their Flex Fuel development facility in Des Plaines, Illinois; UPM in Minnesota supplied and prepared the feedstocks, and characterization of liquid products was conducted in Phillips 66 labs in Oklahoma. The produced gasoline was used for a single-engine emission test at Southwest Research Institute (SwRI®) in San Antonio, TX, as well as in a fleet test at Transportation Research Center, Inc. (TRC Inc.) in East Liberty, Ohio. The project benefited from the use of existing pilot plant equipment at GTI, including a 21.6 bone dry short ton/day gasifier, tar reformer, Morphysorb® acid gas removal, associated syngas cleanup and gasifier feeding and oxygen systems.« less

Utilization of inulin-containing waste in industrial fermentations to produce biofuels and bio-based chemicals.

PubMed

Hughes, Stephen R; Qureshi, Nasib; López-Núñez, Juan Carlos; Jones, Marjorie A; Jarodsky, Joshua M; Galindo-Leva, Luz Ángela; Lindquist, Mitchell R

2017-04-01

Inulins are polysaccharides that belong to an important class of carbohydrates known as fructans and are used by many plants as a means of storing energy. Inulins contain 20 to several thousand fructose units joined by β-2,1 glycosidic bonds, typically with a terminal glucose unit. Plants with high concentrations of inulin include: agave, asparagus, coffee, chicory, dahlia, dandelion, garlic, globe artichoke, Jerusalem artichoke, jicama, onion, wild yam, and yacón. To utilize inulin as its carbon and energy source directly, a microorganism requires an extracellular inulinase to hydrolyze the glycosidic bonds to release fermentable monosaccharides. Inulinase is produced by many microorganisms, including species of Aspergillus, Kluyveromyces, Penicillium, and Pseudomonas. We review various inulinase-producing microorganisms and inulin feedstocks with potential for industrial application as well as biotechnological efforts underway to develop sustainable practices for the disposal of residues from processing inulin-containing crops. A multi-stage biorefinery concept is proposed to convert cellulosic and inulin-containing waste produced at crop processing operations to valuable biofuels and bioproducts using Kluyveromyces marxianus, Yarrowia lipolytica, Rhodotorula glutinis, and Saccharomyces cerevisiae as well as thermochemical treatments.

Strategies for the production of cell wall-deconstructing enzymes in lignocellulosic biomass and their utilization for biofuel production

DOE PAGES

Park, Sang -Hyuck; Ong, Rebecca Garlock; Sticklen, Mariam

2015-12-02

Microbial cell wall-deconstructing enzymes are widely used in the food, wine, pulp and paper, textile, and detergent industries and will be heavily utilized by cellulosic biorefineries in the production of fuels and chemicals. Due to their ability to use freely available solar energy, genetically engineered bioenergy crops provide an attractive alternative to microbial bioreactors for the production of cell wall-deconstructing enzymes. This review article summarizes the efforts made within the last decade on the production of cell wall-deconstructing enzymes in planta for use in the deconstruction of lignocellulosic biomass. A number of strategies have been employed to increase enzyme yieldsmore » and limit negative impacts on plant growth and development including targeting heterologous enzymes into specific subcellular compartments using signal peptides, using tissue-specific or inducible promoters to limit the expression of enzymes to certain portions of the plant or certain times, and fusion of amplification sequences upstream of the coding region to enhance expression. As a result, we also summarize methods that have been used to access and maintain activity of plant-generated enzymes when used in conjunction with thermochemical pretreatments for the production of lignocellulosic biofuels.« less

Biomass in a petrochemical world

PubMed Central

Roddy, Dermot J.

2013-01-01

The world's increasingly voracious appetite for fossil fuels is driven by fast-growing populations and ever-rising aspirations for the lifestyles and standard of living exemplified in the developed world. Forecasts for higher electricity consumption, more comfortable living environments (via heating or cooling) and greater demand for transport fuels are well known. Similar growth in demand is projected for petrochemical-based products in the form of man-made fibres for clothing, ubiquitous plastic artefacts, cosmetics, etc. All drawing upon the same finite oil, gas and coal feedstocks. Biomass can, in principle, substitute for all of these feedstocks. Although ultimately finite, biomass resources can be expanded and renewed if this is a societal priority. This paper examines the projected growth of an energy-intensive international petrochemicals industry, considers its demand for both utilities and feedstocks, and considers the extent to which biomass can substitute for fossil fuels. The scope of this study includes biomass component extraction, direct chemical conversion, thermochemical conversion and biochemical conversion. Noting that the petrochemicals industry consumes around 10 per cent of the world's fossil fuels as feedstocks and almost as much again in utilities, various strategies for addressing future demand are considered. The need for long-term infrastructure and logistics planning is highlighted. PMID:24427511

A sustainable and resilient approach through biochar addition in wood polymer composites.

PubMed

Das, Oisik; Sarmah, Ajit K; Bhattacharyya, Debes

2015-04-15

Biocomposites have been used for sustainability for a few years now and considerable advancements have been made to perfect the physical and mechanical properties. However, there still remain some considerable disadvantages (such as inferior mechanical strength, thickness swell, and rotting) which restrict their proper utilization in wider markets. Attempts have been made to remedy these drawbacks but still further investigation is required to address all the issues and alleviate as many shortcomings as possible. Additionally, concerns related to landfill gas emission prompted the necessity for effective utilization of organic wastes. Lignocellulosic wastes can be valorized by thermo-chemical conversion to form a carbonaceous and renewable material called biochar. Keeping these two problems in mind, a relatively novel idea is recommended for the manufacture of biocomposites where biochar made from pyrolysis of waste could be added with wood and plastic. It is expected to mitigate the general disadvantages of conventional wood plastic composites (WPCs) and at the same time manage landfill wastes giving rise to a potential new breed of improved next generation biocomposites. Furthermore, a 'resilient' perspective is conferred where the long term viability of the state-of-the-art product could be ensured. Copyright © 2015 Elsevier B.V. All rights reserved.

Strategies for the production of cell wall-deconstructing enzymes in lignocellulosic biomass and their utilization for biofuel production

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

Park, Sang -Hyuck; Ong, Rebecca Garlock; Sticklen, Mariam

Microbial cell wall-deconstructing enzymes are widely used in the food, wine, pulp and paper, textile, and detergent industries and will be heavily utilized by cellulosic biorefineries in the production of fuels and chemicals. Due to their ability to use freely available solar energy, genetically engineered bioenergy crops provide an attractive alternative to microbial bioreactors for the production of cell wall-deconstructing enzymes. This review article summarizes the efforts made within the last decade on the production of cell wall-deconstructing enzymes in planta for use in the deconstruction of lignocellulosic biomass. A number of strategies have been employed to increase enzyme yieldsmore » and limit negative impacts on plant growth and development including targeting heterologous enzymes into specific subcellular compartments using signal peptides, using tissue-specific or inducible promoters to limit the expression of enzymes to certain portions of the plant or certain times, and fusion of amplification sequences upstream of the coding region to enhance expression. As a result, we also summarize methods that have been used to access and maintain activity of plant-generated enzymes when used in conjunction with thermochemical pretreatments for the production of lignocellulosic biofuels.« less

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

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

Hahn, David W.

The UF Solar Fuels team has developed a modular reactor at the 10kW scale for the thermochemical conversion of H2O and CO2 to H2 and CO, respectively, using concentrated solar energy to drive high-temperature redox reactions. Various materials, including ferrites, doped and mixed metal ferrites, and ceria, were investigated and reported on. Ceria was chosen as the reactive material, with thermogravimetric and bench-scale analysis concurring with literature review and pointing towards reasonable kinetics and stability at temperatures on the order of 1500 °C. A combined radiation, conduction, and species reaction/mass transport model was developed, utilizing Monte Carlo ray tracing, Latticemore » Boltzmann, and random walk particle tracking for the respective components to direct development and optimization of the reactor. With experimental data used for reaction rates, the model showed a path to efficiencies >20%, which could be market competitive with current PV-hydrolysis hydrogen generation systems. Economic analysis of a larger-scale plant (100kW modular system with cost performed at 500 modules) has been performed, assuming 0.5% and 10% internal rate of return. Without compression costs, H2 production cost using this is technology at $12/kg H2 and $17/kg H2 for realized efficiencies of 20% and 15%, respectively. An interaction of ceria and alumina, with the formation of CeAlO3 occurring at ~1700 °C, had been reported in the literature, but the UF Solar Fuels team observed and reported on it at a large scale, confirming its presence as an engineering consideration when working ceria and alumina at extreme temperatures. CeAlO3 could be being produced at lower temperatures due to the oxidation and reducing environments or due to local hotspots in the reactor. A solar thermogravimeter was developed, to take advantage of the high heating rates available at the UF Solar Simulator Facility to allow investigation of species evolution and material stability in extreme heating rate scenarios. A novel flash-boiling centrifugal-separation steam generator was developed to provide inexpensive, identical steam flows to modular systems, using water-metering and generating the steam for each flow in separate chambers. Several novel methods of reactant material preparation were developed, including: • Sacrificial Pore Formation - Uses a component, such as graphite, designed to be carried away in gaseous form at some point in the preparation process to aid in the formation of pathways and porosity for the enhancement of fluid flow and radiative heat transport at elevated temperatures. • Particle stacking and sintering – Using material that has been pre-sintered (at the temperatures expected for reaction) and mechanically broken apart. The particles are then separated by size to allow the process to be repeated several times with a given particle size range. The resulting stacked and sintered structure maintains micro- to millimeter size pore structure for fluid transport at temperatures that previously demonstrated some contraction or collapse of the reactive material due to porosity reduction due to sintering. In addition, novel seals utilizing graphite and boron nitride particle filler as an internally compressed seal were developed. These seals allow sealing of a ceramic Efficiencies of >4% solar-to-fuel were demonstrated, which at the time of demonstration was the highest yet reported. Hydrogen and CO production rates targets that averaged ~3 cc/gram of reactive material were achieved.« less

Applications of de-oiled microalgal biomass towards development of sustainable biorefinery.

PubMed

Maurya, Rahulkumar; Paliwal, Chetan; Ghosh, Tonmoy; Pancha, Imran; Chokshi, Kaumeel; Mitra, Madhusree; Ghosh, Arup; Mishra, Sandhya

2016-08-01

In view of commercialization of microalgal biofuel, the de-oiled microalgal biomass (DMB) is a surplus by-product in the biorefinery process that needs to be exploited to make the process economically attractive and feasible. This DMB, rich in carbohydrates, proteins, and minerals, can be used as feed, fertilizer, and substrate for the production of bioethanol/bio-methane. Further, thermo-chemical conversion of DMB results into fuels and industrially important chemicals. Future prospects of DMB also lie with its conversion into novel biomaterials like nanoparticles and carbon-dot which have biomedical importance. The lowest valued application of DMB is to use it for adsorption of dyes and heavy metals from industrial effluents. This study reviews how DMB can be utilized for different applications and in the generation of valuable co-products. The value addition of DMB would thereby improve the overall cost economics of the microalgal bio-refinery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Computational Aerothermodynamics in Aeroassist Applications

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.

2001-01-01

Aeroassisted planetary entry uses atmospheric drag to decelerate spacecraft from super-orbital to orbital or suborbital velocities. Numerical simulation of flow fields surrounding these spacecraft during hypersonic atmospheric entry is required to define aerothermal loads. The severe compression in the shock layer in front of the vehicle and subsequent, rapid expansion into the wake are characterized by high temperature, thermo-chemical nonequilibrium processes. Implicit algorithms required for efficient, stable computation of the governing equations involving disparate time scales of convection, diffusion, chemical reactions, and thermal relaxation are discussed. Robust point-implicit strategies are utilized in the initialization phase; less robust but more efficient line-implicit strategies are applied in the endgame. Applications to ballutes (balloon-like decelerators) in the atmospheres of Venus, Mars, Titan, Saturn, and Neptune and a Mars Sample Return Orbiter (MSRO) are featured. Examples are discussed where time-accurate simulation is required to achieve a steady-state solution.

A demonstration of glass bonding using patterned nanocomposite thermites deposited from fluid

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

Rodriguez, Juan Carlos

2015-01-01

Ceramics and other nonmetals are widely used in industrial and research applications. Although these materials provide many advantages, they often pose unique challenges during bonding. This work aims to expand on current processes, which have much narrower applications, to nd a more universal method for nonmetal bonding. We utilize inks comprised of aluminum-based nanoenergetics, (a heat source) and tin (a bonding agent). Requirements for successful bonding are explored and four key criteria are established. Through statistical simulation and thermochemical equilibrium calculations, we conclude that the presence of a diluent in large percentages negatively impacts reaction kinetics. Conversely, we show smallmore » percentages of added tin enhance gas generation and drive faster reaction rates. The bulk bonding material, thermite plus tin, forms a continuous structure during reaction, adhering well to the substrate surface. In some cases, these bonds failed above 1200 kPa.« less

Numerical Modeling of Ablation Heat Transfer

NASA Technical Reports Server (NTRS)

Ewing, Mark E.; Laker, Travis S.; Walker, David T.

2013-01-01

A unique numerical method has been developed for solving one-dimensional ablation heat transfer problems. This paper provides a comprehensive description of the method, along with detailed derivations of the governing equations. This methodology supports solutions for traditional ablation modeling including such effects as heat transfer, material decomposition, pyrolysis gas permeation and heat exchange, and thermochemical surface erosion. The numerical scheme utilizes a control-volume approach with a variable grid to account for surface movement. This method directly supports implementation of nontraditional models such as material swelling and mechanical erosion, extending capabilities for modeling complex ablation phenomena. Verifications of the numerical implementation are provided using analytical solutions, code comparisons, and the method of manufactured solutions. These verifications are used to demonstrate solution accuracy and proper error convergence rates. A simple demonstration of a mechanical erosion (spallation) model is also provided to illustrate the unique capabilities of the method.

JAGUAR Procedures for Detonation Behavior of Silicon Containing Explosives

NASA Astrophysics Data System (ADS)

Stiel, Leonard; Baker, Ernest; Capellos, Christos; Poulos, William; Pincay, Jack

2007-06-01

Improved relationships for the thermodynamic properties of solid and liquid silicon and silicon oxide for use with JAGUAR thermo-chemical equation of state routines were developed in this study. Analyses of experimental melting temperature curves for silicon and silicon oxide indicated complex phase behavior and that improved coefficients were required for solid and liquid thermodynamic properties. Advanced optimization routines were utilized in conjunction with the experimental melting point data to establish volumetric coefficients for these substances. The new property libraries resulted in agreement with available experimental values, including Hugoniot data at elevated pressures. Detonation properties were calculated with JAGUAR using the revised property libraries for silicon containing explosives. Constants of the JWLB equation of state were established for varying extent of silicon reaction. Supporting thermal heat transfer analyses were conducted for varying silicon particle sizes to establish characteristic times for melting and silicon reaction.

Development of life cycle water footprints for the production of fuels and chemicals from algae biomass.

PubMed

Nogueira Junior, Edson; Kumar, Mayank; Pankratz, Stan; Oyedun, Adetoyese Olajire; Kumar, Amit

2018-09-01

This study develops life cycle water footprints for the production of fuels and chemicals via thermochemical conversion of algae biomass. This study is based on two methods of feedstock production - ponds and photobioreactors (PBRs) - and four conversion pathways - fast pyrolysis, hydrothermal liquefaction (HTL), conventional gasification, and hydrothermal gasification (HTG). The results show the high fresh water requirement for algae production and the necessity to recycle harvested water or use alternative water sources. To produce 1 kg of algae through ponds, 1564 L of water are required. When PBRs are used, only 372 L water are required; however, the energy requirements for PBRs are about 30 times higher than for ponds. From a final product perspective, the pathway based on the gasification of algae biomass was the thermochemical conversion method that required the highest amount of water per MJ produced (mainly due to its low hydrogen yield), followed by fast pyrolysis and HTL. On the other hand, HTG has the lowest water footprint, mainly because the large amount of electricity generated as part of the process compensates for the electricity used by the system. Performance in all pathways can be improved through recycling channels. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of sodium carbonate catalyst weight on production of bio-oil via thermochemical liquefaction of corncobs in ethanol-water solution

NASA Astrophysics Data System (ADS)

Sembodo, Bregas Siswahjono Tatag; Sulistyo, Hary; Sediawan, Wahyudi Budi; Fahrurrozi, Mohammad

2018-02-01

Lignocellulosic biomass has recently received serious attention as an energy source that can replace fossil fuels. Corncob is one of lignocellulosic biomass wastes, which can be further processed into bio-oil through thermochemical liquefaction process. Bio-oil is expected to be further processed into fuel oil. In this research the effect of Na2CO3 catalyst weight on the yield of bio-oil was investigated. The composition of bio-oil produced in this process was analyzed by GC-MS. Bio-oil formation rate were analyzed through mathematical model development. First model aasumed as an isothermal process, while second model was not. It is found that both models were able to provide a good approach to experimental data. The average reaction rate constants was obtained from isothermal model, while the activation energy level and collision factors were obtained from non-isothermal model. The reaction rate will increase by addition of Na2CO3 (0 - 0.5 g) as catalyst to 250 mL system solution, then the activation energy will decrease from 1964.265 joules/mole to 1029.994 joules/mole. The GC-MS analysis results showed that the bio-oil were contained of ester compounds, phenolic compounds, cyclic compunds, heterocyclic compounds, and poly-alcohols compounds.

Production of biofuel using molluscan pseudofeces derived from algal cells

DOEpatents

Das, Keshav C.; Chinnasamy, Senthil; Shelton, James; Wilde, Susan B.; Haynie, Rebecca S.; Herrin, James A.

2012-08-28

Embodiments of the present disclosure provide for novel strategies to harvest algal lipids using mollusks which after feeding algae from the growth medium can convert algal lipids into their biomass or excrete lipids in their pseudofeces which makes algae harvesting energy efficient and cost effective. The bioconverter, filter-feeding mollusks and their pseudofeces can be harvested and converted to biocrude using an advanced thermochemical liquefaction technology. Methods, systems, and materials are disclosed for the harvest and isolation of algal lipids from the mollusks, molluscan feces and molluscan pseudofeces.

Thermochemical and Kinetics of Hydrazine Dehydrogenation by an Oxygen Atom in Hydrazine-Rich Systems: A Dimer Model.

PubMed

Spada, Rene F K; Ferrão, Luiz F A; Roberto-Neto, Orlando; Lischka, Hans; Machado, Francisco B C

2015-12-24

The kinetics of the reaction of N2H4 with oxygen depends sensitively on the initial conditions used. In oxygen-rich systems, the rate constant shows a conventional positive temperature dependence, while in hydrazine-rich setups the dependence is negative in certain temperature ranges. In this study, a theoretical model is presented that adequately reproduces the experimental results trend and values for hydrazine-rich environment, consisting of the hydrogen abstraction from the hydrazine (N2H4) dimer by an oxygen atom. The thermochemical properties of the reaction were computed using two quantum chemical approaches, the coupled cluster theory with single, double, and noniterative triple excitations (CCSD(T)) and the M06-2X DFT approach with the aug-cc-pVTZ and the maug-cc-pVTZ basis sets, respectively. The kinetic data were calculated with the improved canonical variational theory (ICVT) using a dual-level methodology to build the reaction path. The tunneling effects were considered by means of the small curvature tunneling (SCT) approximation. Potential wells on both sides of the reaction ((N2H4)2 + O → N2H4···N2H3 + OH) were determined. A reaction path with a negative activation energy was found leading, in the temperature range of 250-423 K, to a negative dependence of the rate constant on the temperature, which is in good agreement with the experimental measurements. Therefore, the consideration of the hydrazine dimer model provides significantly improved agreement with the experimental data and should be included in the mechanism of the global N2H4 combustion process, as it can be particularly important in hydrazine-rich systems.

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.

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 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.

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

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

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.

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.

Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

NASA Technical Reports Server (NTRS)

T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor); Huang, Cunping (Inventor)

2014-01-01

Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

Multiscale modeling and experimental interpretation of perovskite oxide materials in thermochemical energy storage and conversion for application in concentrating solar power

NASA Astrophysics Data System (ADS)

Albrecht, Kevin J.

Decarbonization of the electric grid is fundamentally limited by the intermittency of renewable resources such as wind and solar. Therefore, energy storage will play a significant role in the future of grid-scale energy generation to overcome the intermittency issues. For this reason, concentrating solar power (CSP) plants have been a renewable energy generation technology of interest due to their ability to participate in cost effective and efficient thermal energy storage. However, the ability to dynamically dispatch a CSP plant to meet energy demands is currently limited by the large quantities of sensible thermal energy storage material needed in a molten salt plant. Perovskite oxides have been suggested as a thermochemical energy storage material to enhance the energy storage capabilities of particle-based CSP plants, which combine sensible and chemical modes of energy storage. In this dissertation, computational models are used to establish the thermochemical energy storage potential of select perovskite compositions, identify system configurations that promote high values of energy storage and solar-to-electric efficiency, assess the kinetic and transport limitation of the chemical mode of energy storage, and create receiver and reoxidation reactor models capable of aiding in component design. A methodology for determining perovskite thermochemical energy storage potential is developed based on point defect models to represent perovskite non-stoichiometry as a function of temperature and gas phase oxygen partial pressure. The thermodynamic parameters necessary for the model are extracted from non-stoichiometry measurements by fitting the model using an optimization routine. The procedure is demonstrated for Ca0.9Sr0.1MnO 3-d which displayed combined energy storage values of 705.7 kJ/kg -1 by cycling between 773 K and 0.21 bar oxygen to 1173 K and 10 -4 bar oxygen. Thermodynamic system-level models capable of exploiting perovskite redox chemistry for energy storage in CSP plants are presented. Comparisons of sweep gas and vacuum pumping reduction as well as hot storage conditions indicate that solar-to-electric efficiencies are higher for sweep gas reduction system at equivalent values of energy storage if the energy parasitics of commercially available devices are considered. However, if vacuum pump efficiency between 15% and 30% can be achieved, the reduction methods will be approximately equal. Reducing condition oxygen partial pressures below 10-3 bar for sweep gas reduction and 10-2 bar for vacuum pumping reduction result in large electrical parasitics, which significantly reduce solar-to-electric efficiency. A model based interpretation of experimental measurements made for perovskite redox cycling using sweep gas in a packed bed is presented. The model indicates that long reduction times for equilibrating perovskites with low oxygen partial pressure sweep gas, compared to reoxidation, are primarily due to the oxygen carrying capacity of high purity sweep gas and not surface kinetic limitations. Therefore, achieving rapid reduction in the limited receiver residence time will be controlled by the quantity of sweep gas introduced. Effective kinetic parameters considering surface reaction and radial particle diffusion are fit to the experimental data. Variable order rate expressions without significant particle radial diffusion limitations are shown to be capable of representing the reduction and oxidation data. Modeling of a particle reduction receiver using continuous flow of perovskite solid and sweep gas in counter-flow configuration has identified issues with managing the oxygen evolved by the solid as well as sweep gas flow rates. Introducing sweep gas quantities necessary for equilibrating the solid with oxygen partial pressures below 10-2 are shown to result in gas phase velocities above the entrainment velocity of 500 um particles. Receiver designs with considerations for gas management are investigated and the results indicate that degrees of reduction corresponding to only oxygen partial pressures of 10-2 bar are attained. Numerical investigation into perovskite thermochemical energy storage indicates that achieving high levels of reduction through sweep gas or vacuum pumping to lower gas phase oxygen partial pressure below 10-2 bar display issues with parasitic energy consumption and gas phase management. Therefore, focus on material development should place a premium on thermal reduction and reduction by shifting oxygen partial pressure between ambient and 10-2 bar. Such a material would enable the development of a system with high solar-to-electric efficiencies and degrees of reduction which are attainable in realistic component geometries.

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

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

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.

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.

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.

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

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.

Applications of plasma core reactors to terrestrial energy systems

NASA Technical Reports Server (NTRS)

Latham, T. S.; Biancardi, F. R.; Rodgers, R. J.

1974-01-01

Plasma core reactors offer several new options for future energy needs in addition to space power and propulsion applications. Power extraction from plasma core reactors with gaseous nuclear fuel allows operation at temperatures higher than conventional reactors. Highly efficient thermodynamic cycles and applications employing direct coupling of radiant energy are possible. Conceptual configurations of plasma core reactors for terrestrial applications are described. Closed-cycle gas turbines, MHD systems, photo- and thermo-chemical hydrogen production processes, and laser systems using plasma core reactors as prime energy sources are considered. Cycle efficiencies in the range of 50 to 65 percent are calculated for closed-cycle gas turbine and MHD electrical generators. Reactor advantages include continuous fuel reprocessing which limits inventory of radioactive by-products and thorium-U-233 breeder configurations with about 5-year doubling times.-

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

Solar Thermo-coupled Electrochemical Oxidation of Aniline in Wastewater for the Complete Mineralization Beyond an Anodic Passivation Film.

PubMed

Yuan, Dandan; Tian, Lei; Li, Zhida; Jiang, Hong; Yan, Chao; Dong, Jing; Wu, Hongjun; Wang, Baohui

2018-02-15

Herein, we report the solar thermal electrochemical process (STEP) aniline oxidation in wastewater for totally solving the two key obstacles of the huge energy consumption and passivation film in the electrochemical treatment. The process, fully driven by solar energy without input of any other energies, sustainably serves as an efficient thermoelectrochemical oxidation of aniline by the control of the thermochemical and electrochemical coordination. The thermocoupled electrochemical oxidation of aniline achieved a fast rate and high efficiency for the full minimization of aniline to CO 2 with the stability of the electrode and without formation of polyaniline (PAN) passivation film. A clear mechanism of aniline oxidation indicated a switching of the reactive pathway by the STEP process. Due to the coupling of solar thermochemistry and electrochemistry, the electrochemical current remained stable, significantly improving the oxidation efficiency and mineralization rate by apparently decreasing the electrolytic potential when applied with high temperature. The oxidation rate of aniline and chemical oxygen demand (COD) removal rate could be lifted up to 2.03 and 2.47 times magnification compared to conventional electrolysis, respectively. We demonstrate that solar-driven STEP processes are capable of completely mineralizing aniline with high utilization of solar energy. STEP aniline oxidation can be utilized as a green, sustainable water treatment.

Food waste-to-energy conversion technologies: current status and future directions.

PubMed

Pham, Thi Phuong Thuy; Kaushik, Rajni; Parshetti, Ganesh K; Mahmood, Russell; Balasubramanian, Rajasekhar

2015-04-01

Food waste represents a significantly fraction of municipal solid waste. Proper management and recycling of huge volumes of food waste are required to reduce its environmental burdens and to minimize risks to human health. Food waste is indeed an untapped resource with great potential for energy production. Utilization of food waste for energy conversion currently represents a challenge due to various reasons. These include its inherent heterogeneously variable compositions, high moisture contents and low calorific value, which constitute an impediment for the development of robust, large scale, and efficient industrial processes. Although a considerable amount of research has been carried out on the conversion of food waste to renewable energy, there is a lack of comprehensive and systematic reviews of the published literature. The present review synthesizes the current knowledge available in the use of technologies for food-waste-to-energy conversion involving biological (e.g. anaerobic digestion and fermentation), thermal and thermochemical technologies (e.g. incineration, pyrolysis, gasification and hydrothermal oxidation). The competitive advantages of these technologies as well as the challenges associated with them are discussed. In addition, the future directions for more effective utilization of food waste for renewable energy generation are suggested from an interdisciplinary perspective. Copyright © 2014 Elsevier Ltd. All rights reserved.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater.

PubMed

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-03-15

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO 2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

PubMed Central

Gu, Di; Gao, Simeng; Jiang, TingTing; Wang, Baohui

2017-01-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process. PMID:28294180

Solar-mediated thermo-electrochemical oxidation of sodium dodecyl benzene sulfonate by modulating the effective oxidation potential and pathway for green remediation of wastewater

NASA Astrophysics Data System (ADS)

Gu, Di; Gao, Simeng; Jiang, Tingting; Wang, Baohui

2017-03-01

To match the relentless pursuit of three research hot points - efficient solar utilization, green and sustainable remediation of wastewater and advanced oxidation processes, solar-mediated thermo-electrochemical oxidation of surfactant was proposed and developed for green remediation of surfactant wastewater. The solar thermal electrochemical process (STEP), fully driven with solar energy to electric energy and heat and without an input of other energy, sustainably serves as efficient thermo-electrochemical oxidation of surfactant, exemplified by SDBS, in wastewater with the synergistic production of hydrogen. The electrooxidation-resistant surfactant is thermo-electrochemically oxidized to CO2 while hydrogen gas is generated by lowing effective oxidation potential and suppressing the oxidation activation energy originated from the combination of thermochemical and electrochemical effect. A clear conclusion on the mechanism of SDBS degradation can be proposed and discussed based on the theoretical analysis of electrochemical potential by quantum chemical method and experimental analysis of the CV, TG, GC, FT-IR, UV-vis, Fluorescence spectra and TOC. The degradation data provide a pilot for the treatment of SDBS wastewater that appears to occur via desulfonation followed by aromatic-ring opening. The solar thermal utilization that can initiate the desulfonation and activation of SDBS becomes one key step in the degradation process.

Bubbling bed catalytic hydropyrolysis process utilizing larger catalyst particles and smaller biomass particles featuring an anti-slugging reactor

DOEpatents

Marker, Terry L; Felix, Larry G; Linck, Martin B; Roberts, Michael J

2014-09-23

This invention relates to a process for thermochemically transforming biomass or other oxygenated feedstocks into high quality liquid hydrocarbon fuels. In particular, a catalytic hydropyrolysis reactor, containing a deep bed of fluidized catalyst particles is utilized to accept particles of biomass or other oxygenated feedstocks that are significantly smaller than the particles of catalyst in the fluidized bed. The reactor features an insert or other structure disposed within the reactor vessel that inhibits slugging of the bed and thereby minimizes attrition of the catalyst. Within the bed, the biomass feedstock is converted into a vapor-phase product, containing hydrocarbon molecules and other process vapors, and an entrained solid char product, which is separated from the vapor stream after the vapor stream has been exhausted from the top of the reactor. When the product vapor stream is cooled to ambient temperatures, a significant proportion of the hydrocarbons in the product vapor stream can be recovered as a liquid stream of hydrophobic hydrocarbons, with properties consistent with those of gasoline, kerosene, and diesel fuel. Separate streams of gasoline, kerosene, and diesel fuel may also be obtained, either via selective condensation of each type of fuel, or via later distillation of the combined hydrocarbon liquid.

Bioconversion study conducted by JPL

NASA Technical Reports Server (NTRS)

Kalvinskas, J.

1978-01-01

The Jet Propulsion Laboratory (JPL) of Caltech conducted a study of bioconversion as a means of identifying the role of biomass for meeting the national energy fuel and chemical requirements and the role and means for JPL-Caltech involvement in bioconversion. The bioconversion study included the following categories; biomass sources, chemicals from biomass, thermochemical conversion of biomass to fuels, biological conversion of biomass to fuels and chemicals, and basic bioconversion sciences. A detailed review is included of the bioconversion fields cited with specific conclusions and recommendations given for future research and development and overall biomass system engineering and economic studies.

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

Material Analysis of Coated Siliconized Silicon Carbide (SiSiC) Honeycomb Structures for Thermochemical Hydrogen Production

PubMed Central

Neises-von Puttkamer, Martina; Simon, Heike; Schmücker, Martin; Roeb, Martin; Sattler, Christian; Pitz-Paal, Robert

2013-01-01

In the present work, thermochemical water splitting with siliconized silicon carbide (SiSiC) honeycombs coated with a zinc ferrite redox material was investigated. The small scale coated monoliths were tested in a laboratory test-rig and characterized by X-ray diffractometry (XRD) and Scanning Electron Microscopy (SEM) with corresponding micro analysis after testing in order to characterize the changes in morphology and composition. Comparison of several treated monoliths revealed the formation of various reaction products such as SiO2, zircon (ZrSiO4), iron silicide (FeSi) and hercynite (FeAl2O4) indicating the occurrence of various side reactions between the different phases of the coating as well as between the coating and the SiSiC substrate. The investigations showed that the ferrite is mainly reduced through reaction with silicon (Si), which is present in the SiSiC matrix, and silicon carbide (SiC). These results led to the formulation of a new redox mechanism for this system in which Zn-ferrite is reduced through Si forming silicon dioxide (SiO2) and through SiC forming SiO2 and carbon monoxide. A decline of hydrogen production within the first 20 cycles is suggested to be due to the growth of a silicon dioxide and zircon layer which acts as a diffusion barrier for the reacting specie. PMID:28809316

Material Analysis of Coated Siliconized Silicon Carbide (SiSiC) Honeycomb Structures for Thermochemical Hydrogen Production.

PubMed

Neises-von Puttkamer, Martina; Simon, Heike; Schmücker, Martin; Roeb, Martin; Sattler, Christian; Pitz-Paal, Robert

2013-01-31

In the present work, thermochemical water splitting with siliconized silicon carbide (SiSiC) honeycombs coated with a zinc ferrite redox material was investigated. The small scale coated monoliths were tested in a laboratory test-rig and characterized by X-ray diffractometry (XRD) and Scanning Electron Microscopy (SEM) with corresponding micro analysis after testing in order to characterize the changes in morphology and composition. Comparison of several treated monoliths revealed the formation of various reaction products such as SiO₂, zircon (ZrSiO₄), iron silicide (FeSi) and hercynite (FeAl₂O₄) indicating the occurrence of various side reactions between the different phases of the coating as well as between the coating and the SiSiC substrate. The investigations showed that the ferrite is mainly reduced through reaction with silicon (Si), which is present in the SiSiC matrix, and silicon carbide (SiC). These results led to the formulation of a new redox mechanism for this system in which Zn-ferrite is reduced through Si forming silicon dioxide (SiO₂) and through SiC forming SiO₂ and carbon monoxide. A decline of hydrogen production within the first 20 cycles is suggested to be due to the growth of a silicon dioxide and zircon layer which acts as a diffusion barrier for the reacting specie.

Design and commissioning of a multi-mode prototype for thermochemical conversion of human faeces.

PubMed

Jurado, Nelia; Somorin, Tosin; Kolios, Athanasios J; Wagland, Stuart; Patchigolla, Kumar; Fidalgo, Beatriz; Parker, Alison; McAdam, Ewan; Williams, Leon; Tyrrel, Sean

2018-05-01

This article describes the design and commissioning of a micro-combustor for energy recovery from human faeces, which can operate both in updraft and downdraft modes. Energy recovery from faecal matter via thermochemical conversion has recently been identified as a feasible solution for sanitation problems in low income countries and locations of high income countries where access to sewage infrastructures is difficult or not possible. This technology can be applied to waterless toilets with the additional outcome of generating heat and power that can be used to pre-treat the faeces before their combustion and to ensure that the entire system is self-sustaining. The work presented here is framed within the Nano Membrane Toilet (NMT) project that is being carried out at Cranfield University, as part of the Reinvent the Toilet Challenge of the Bill and Melinda Gates Foundation. For this study, preliminary trials using simulant faeces pellets were first carried out to find out the optimum values for the main operating variables at the scale required by the process, i.e. a fuel flowrate between 0.4 and 1.2 g/min of dry faeces. Parameters such as ignition temperature, residence time, and maximum temperature reached, were determined and used for the final design of the bench-scale combustor prototype. The prototype was successfully commissioned and the first experimental results, using real human faeces, are discussed in the paper.

Numerical study on the thermo-chemically driven Geodynamo

NASA Astrophysics Data System (ADS)

Trümper, Tobias; Hansen, Ulrich

2014-05-01

In our numerical study we consider magneto-convection in the Earth's outer core driven by buoyancy induced by heterogeneities both in the thermal and the chemical field. The outer core is thus treated as a self-gravitating, rotating, spherical shell with unstable thermal and chemical gradients across its radius. The thermal gradient is maintained by secular cooling of the core and the release of latent heat at the inner core freezing front. Simultaneously, the concentration of the light constituents of the liquid phase increases at the inner core boundary since only a smaller fraction of the light elements can be incorporated during solidification. Thus, the inner core boundary constitutes a source of compositional buoyancy. The molecular diffusivities of the driving agents differ by some orders of magnitude so that a double-diffusive model is employed in order to study the flow dynamics of this system. We investigate the influence of different thermo-chemical driving scenarios on the structure of the flow and the internal magnetic field. A constant ratio of the diffusivities (Le=10) and a constant Ekman number (Ek=10-4) are adopted. Apart from testing different driving scenarios, the double-diffusive approach also allows to implement distinct boundary conditions on temperature and composition. Isochemical and fixed chemical flux boundary conditions are implemented in order to investigate their respective influence on the flow and magnetic field generation.

A theoretical thermochemical study of solute-solvent dielectric effects in the displacement of codon-anticodon base pairs

NASA Astrophysics Data System (ADS)

Monajjemi, M.; Razavian, M. H.; Mollaamin, F.; Naderi, F.; Honarparvar, B.

2008-12-01

Quantum-chemical solvent effect theories describe the electronic structure of a molecular subsystem embedded in a solvent or other molecular environment. The solvation of biomolecules is important in molecular biology, since numerous processes involve proteins interacting in changing solvent-solute systems. In this theoretical study, we focus on mRNA-tRNA base pairs as a fundamental step in protein synthesis influenced by hydrogen bonding between two antiparallel trinucleotides, namely, the mRNA codon and tRNA anticodon. We use the mean reaction field theories, which describe electrostatic and polarization interactions between solute and solvent in the AAA, UUU, AAG, and UUC triplex sequences optimized in various solvent media such as water, dimethylsulfoxide, methanol, ethanol, and cyclopean using the self-consistent reaction field model. This process depends on either the reaction potential function of the solvent or charge transfer operators that appear in solute-solvent interaction. Because of codon and anticodon biological criteria, we performed nonempirical quantum-mechanical calculations at the BLYP and B3LYP/3-21G, 6-31G, and 6-31G* levels of theory in the gas phase and five solvents at three temperatures. Finally, to obtain more information, we calculated thermochemical parameters to find that the dielectric constant of solvents plays an important role in the displacement of amino acid sequences on codon-anticodon residues in proteins, which can cause some mutations in humans.

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.

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.

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.

SolarSyngas: Results from a virtual institute developing materials and key components for solar thermochemical fuel production

NASA Astrophysics Data System (ADS)

Roeb, Martin; Steinfeld, Aldo; Borchardt, Günter; Feldmann, Claus; Schmücker, Martin; Sattler, Christian; Pitz-Paal, Robert

2016-05-01

The Helmholtz Virtual Institute (VI) SolarSynGas brings together expertise from solar energy research and materials science to develop metal oxide based redox materials and to integrate them in a suitable way into related process technologies for two-step thermochemical production of hydrogen and carbon monoxide from water and CO2. One of the foci of experimental investigation was exploring the impact of doping on the feasibility of ceria-based materials - mainly by Zr-doping. The results indicate that a certain Zr-content enhances the reducibility and therefore the splitting performance. Increasing the Zr-content to x = 0.15 improved the specific CO2-splitting performance by 50% compared to pure ceria. This finding agrees with theoretical studies attributing the improvements to lattice modification caused by the introduction of Zr4+. Thermogravimetric relaxation experiments and equilibrium oxygen isotope exchange experiments with subsequent depth profiling analysis were carried out on ceria. As a result the reduction reaction of even dense samples of pure ceria with a grain size of about 20 µm is surface reaction controlled. The structure of the derived expression for the apparent activation energy suggests that the chemical surface exchange coefficient should show only a very weak dependence on temperature for ceria doped with lower valence cations. A solar receiver reactor exhibiting a foam-type reticulated porous ceramics made of ceria was tested. It could be shown that applying dual-scale porosity to those foams with mm-size pores for effective radiative heat transfer during reduction and μm-size pores within its struts for enhanced kinetics during oxidation allows enhancing the performance of the reactor significantly. Also a particle process concept applying solid-solid heat recovery from redox particles in a high temperature solar thermochemical process was analysed that uses ceramic spheres as solid heat transfer medium. This concept can be implemented into any particle reactor and offers sufficiently high heat recovery rates and thus high overall system efficiencies. A detailed model to calculate the performance of the concept in consideration of temperature dependent material data and several other influencing factors was developed. It was found that the molar flow ratio needs to be optimized regarding the contact time and the heat recovery rate only increases slightly over a contact time of τ=10s. The system reaches a heat recovery rate over 70% in case of six stages, connected in a quasi-counter-current principle.

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, Paul W.; Bannister, Ronald L.

1995-01-01

A gas turbine system in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas.

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.

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.

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.

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

Bio-Oil Separation and Stabilization by Supercritical Fluid Fractionation. 2014 Final Report

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

Agblevor, Foster; Petkovic, Lucia; Bennion, Edward

The objective of this project is to use supercritical fluids to separate and fractionate algal-based bio-oils into stable products that can be subsequently upgraded to produce drop-in renewable fuels. To accomplish this objective, algae was grown and thermochemically converted to bio-oils using hydrothermal liquefaction (HTL), pyrolysis, and catalytic pyrolysis. The bio-oils were separated into an extract and a raffinate using near-critical propane or carbon dioxide. The fractions were then subjected to thermal aging studies to determine if the extraction process had stabilized the products. It was found that the propane extract fraction was twice as stable as the parent catalyticmore » pyrolysis bio-oils as measured by the change in viscosity after two weeks of accelerated aging at 80°C. Further, in-situ NMR aging studies found that the propane extract was chemically more stable than the parent bio-oil. Thus the milestone of stabilizing the product was met. A preliminary design of the extraction plant was prepared. The design was based on a depot scale plant processing 20,000,000 gallons per year of bio-oil. It was estimated that the capital costs for such a plant would be $8,700,000 with an operating cost of $3,500,000 per year. On a per gallon of product cost and a 10% annual rate of return, capital costs would represent $0.06 per gallon and operating costs would amount to $0.20 per gallon. Further, it was found that the energy required to run the process represented 6.2% of the energy available in the bio-oil, meeting the milestone of less than 20%. Life cycle analysis and greenhouse gas (GHG) emission analysis found that the energy for running the critical fluid separation process and the GHG emissions were minor compared to all the inputs to the overall well to pump system. For the well to pump system boundary, energetics in biofuel conversion are typically dominated by energy demands in the growth, dewater, and thermochemical process. Bio-oil stabilization by near critical propane extraction had minimal impact in the overall energetics of the process with NER contributions of 0.03. Based on the LCA, the overall conversion pathways were found to be energy intensive with a NER of about 2.3 and 1.2 for catalytic pyrolysis and HTL, respectively. GHG emissions for the catalytic pyrolysis process were greater than that of petroleum diesel at 210 g CO2 eq compared to 18.9 g CO2 eq. Microalgae bio-oil based diesel with thermochemical conversion through HTL meets renewable fuel standards with favorable emission reductions of -10.8 g CO2 eq. The importance of the outcomes is that the critical fluid extraction and stabilization process improved product stability and did so with minimal energy inputs and processing costs. The LCA and GHG emission calculations point toward the HTL pathway as the more favorable thermochemical route towards upgrading algae to bio-fuels. Since the quality of the HTL oil was significantly lower than that of the catalytic pyrolysis bio-oil, the next steps point toward improving the quality of the HTL oils from algae biomass and focusing the critical fluid stabilization on that bio-oil product.« less

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

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

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Scaling up of renewable chemicals.

PubMed

Sanford, Karl; Chotani, Gopal; Danielson, Nathan; Zahn, James A

2016-04-01

The transition of promising technologies for production of renewable chemicals from a laboratory scale to commercial scale is often difficult and expensive. As a result the timeframe estimated for commercialization is typically underestimated resulting in much slower penetration of these promising new methods and products into the chemical industries. The theme of 'sugar is the next oil' connects biological, chemical, and thermochemical conversions of renewable feedstocks to products that are drop-in replacements for petroleum derived chemicals or are new to market chemicals/materials. The latter typically offer a functionality advantage and can command higher prices that result in less severe scale-up challenges. However, for drop-in replacements, price is of paramount importance and competitive capital and operating expenditures are a prerequisite for success. Hence, scale-up of relevant technologies must be interfaced with effective and efficient management of both cell and steel factories. Details involved in all aspects of manufacturing, such as utilities, sterility, product recovery and purification, regulatory requirements, and emissions must be managed successfully. Copyright © 2016 Elsevier Ltd. All rights reserved.

Time-Resolved Kinetic Chirped-Pulse Rotational Spectroscopy in a Room-Temperature Flow Reactor

DOE PAGES

Zaleski, Daniel P.; Harding, Lawrence B.; Klippenstein, Stephen J.; ...

2017-12-01

Chirped-pulse Fourier transform millimeter-wave spectroscopy is a potentially powerful tool for studying chemical reaction dynamics and kinetics. Branching ratios of multiple reaction products and intermediates can be measured with unprecedented chemical specificity; molecular isomers, conformers, and vibrational states have distinct rotational spectra. Here we demonstrate chirped-pulse spectroscopy of vinyl cyanide photoproducts in a flow tube reactor at ambient temperature of 295 K and pressures of 1-10 mu bar. This in situ and time-resolved experiment illustrates the utility of this novel approach to investigating chemical reaction dynamics and kinetics. Following 193 nm photodissociation of CH2CHCN, we observe rotational relaxation of energizedmore » HCN, HNC, and HCCCN photoproducts with 10 mu s time resolution and sample the vibrational population distribution of HCCCN. The experimental branching ratio HCN/HCCCN is compared with a model based on RRKM theory using high-level ab initio calculations, which were in turn validated by comparisons to Active Thermochemical Tables enthalpies.« less

Upgrading agricultural wastes using three different carbonization methods: Thermal, hydrothermal and vapothermal.

PubMed

Yeoh, Keat-Hor; Shafie, S A; Al-Attab, K A; Zainal, Z A

2018-06-15

In this study, three different methods for high quality solid fuel production were tested and compared experimentally. Oil palm empty fruit bunches, mesocarp fibers, palm kernel shells and rubber seeds shells were treated using thermal (TC), hydrothermal (HTC) and vapothermal (VTC) carbonization. All thermochemical methods were accomplished by using a custom made batch-type reactor. Utilization of novel single reactor equipped with suspended internal container provided efficient operation since both steam generator and raw materials were placed inside the same reactor. Highest energy densification was achieved by VTC process followed by TC and HTC processes. The heating value enhancement in VTC and TC was achieved by the increase in fixed carbon content and reduction in volatile matter. The formation of the spherical components in HTC hydrochar which gave a sharp peak at 340 °C in the DTG curves was suggested as the reason that led to the increment in energy content. Copyright © 2018 Elsevier Ltd. All rights reserved.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

Utilization of grasses for potential biofuel production and phytoremediation of heavy metal contaminated soils.

PubMed

Balsamo, Ronald A; Kelly, William J; Satrio, Justinus A; Ruiz-Felix, M Nydia; Fetterman, Marisa; Wynn, Rodd; Hagel, Kristen

2015-01-01

This research focuses on investigating the use of common biofuel grasses to assess their potential as agents of long-term remediation of contaminated soils using lead as a model heavy metal ion. We present evidence demonstrating that switch grass and Timothy grass may be potentially useful for long-term phytoremediation of heavy metal contaminated soils and describe novel techniques to track and remove contaminants from inception to useful product. Enzymatic digestion and thermochemical approaches are being used to convert this lignocellulosic feedstock into useful product (sugars, ethanol, biocrude oil+biochar). Preliminary studies on enzymatic hydrolysis and fast pyrolysis of the Switchgrass materials that were grown in heavy metal contaminated soil and non-contaminated soils show that the presence of lead in the Switchgrass material feedstock does not adversely affect the outcomes of the conversion processes. These results indicate that the modest levels of contaminant uptake allow these grass species to serve as phytoremediation agents as well as feedstocks for biofuel production in areas degraded by industrial pollution.

Predictive performance modeling framework for a novel enclosed particle receiver configuration and application for thermochemical energy storage

DOE PAGES

Martinek, Janna; Wendelin, Timothy; Ma, Zhiwen

2018-04-05

Concentrating solar power (CSP) plants can provide dispatchable power with a thermal energy storage capability for increased renewable-energy grid penetration. Particle-based CSP systems permit higher temperatures, and thus, potentially higher solar-to-electric efficiency than state-of-the-art molten-salt heat-transfer systems. This paper describes a detailed numerical analysis framework for estimating the performance of a novel, geometrically complex, enclosed particle receiver design. The receiver configuration uses arrays of small tubular absorbers to collect and subsequently transfer solar energy to a flowing particulate medium. The enclosed nature of the receiver design renders it amenable to either an inert heat-transfer medium, or a reactive heat-transfer medium that requires a controllable ambient environment. The numerical analysis framework described in this study is demonstrated for the case of thermal reduction of CaCr 0.1Mn 0.9O 3-more » $$\\delta$$ for thermochemical energy storage. The modeling strategy consists of Monte Carlo ray tracing for absorbed solar-energy distributions from a surround heliostat field, computational fluid dynamics modeling of small-scale local tubular arrays, surrogate response surfaces that approximately capture simulated tubular array performance, a quasi-two-dimensional reduced-order description of counter-flow reactive solids and purge gas, and a radiative exchange model applied to embedded-cavity structures at the size scale of the full receiver. In this work we apply the numerical analysis strategy to a single receiver configuration, but the framework can be generically applicable to alternative enclosed designs. In conclusion, we assess sensitivity of receiver performance to surface optical properties, heat-transfer coefficients, solids outlet temperature, and purge-gas feed rates, and discuss the significance of model assumptions and results for future receiver development.« less

Predictive performance modeling framework for a novel enclosed particle receiver configuration and application for thermochemical energy storage

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

Martinek, Janna; Wendelin, Timothy; Ma, Zhiwen

Concentrating solar power (CSP) plants can provide dispatchable power with a thermal energy storage capability for increased renewable-energy grid penetration. Particle-based CSP systems permit higher temperatures, and thus, potentially higher solar-to-electric efficiency than state-of-the-art molten-salt heat-transfer systems. This paper describes a detailed numerical analysis framework for estimating the performance of a novel, geometrically complex, enclosed particle receiver design. The receiver configuration uses arrays of small tubular absorbers to collect and subsequently transfer solar energy to a flowing particulate medium. The enclosed nature of the receiver design renders it amenable to either an inert heat-transfer medium, or a reactive heat-transfer medium that requires a controllable ambient environment. The numerical analysis framework described in this study is demonstrated for the case of thermal reduction of CaCr 0.1Mn 0.9O 3-more » $$\\delta$$ for thermochemical energy storage. The modeling strategy consists of Monte Carlo ray tracing for absorbed solar-energy distributions from a surround heliostat field, computational fluid dynamics modeling of small-scale local tubular arrays, surrogate response surfaces that approximately capture simulated tubular array performance, a quasi-two-dimensional reduced-order description of counter-flow reactive solids and purge gas, and a radiative exchange model applied to embedded-cavity structures at the size scale of the full receiver. In this work we apply the numerical analysis strategy to a single receiver configuration, but the framework can be generically applicable to alternative enclosed designs. In conclusion, we assess sensitivity of receiver performance to surface optical properties, heat-transfer coefficients, solids outlet temperature, and purge-gas feed rates, and discuss the significance of model assumptions and results for future receiver development.« less

Application of a reversible chemical reaction system to solar thermal power plants

NASA Technical Reports Server (NTRS)

Hanseth, E. J.; Won, Y. S.; Seibowitz, L. P.

1980-01-01

Three distributed dish solar thermal power systems using various applications of SO2/SO3 chemical energy storage and transport technology were comparatively assessed. Each system features various roles for the chemical system: (1) energy storage only, (2) energy transport, or (3) energy transport and storage. These three systems were also compared with the dish-Stirling, using electrical transport and battery storage, and the central receiver Rankine system, with thermal storage, to determine the relative merit of plants employing a thermochemical system. As an assessment criterion, the busbar energy costs were compared. Separate but comparable solar energy cost computer codes were used for distributed receiver and central receiver systems. Calculations were performed for capacity factors ranging from 0.4 to 0.8. The results indicate that SO2/SO3 technology has the potential to be more cost effective in transporting the collected energy than in storing the energy for the storage capacity range studied (2-15 hours)

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

The search for and analysis of direct samples of early Solar System aqueous fluids.

PubMed

Zolensky, Michael E; Bodnar, Robert J; Yurimoto, Hisayoshi; Itoh, Shoichi; Fries, Marc; Steele, Andrew; Chan, Queenie H-S; Tsuchiyama, Akira; Kebukawa, Yoko; Ito, Motoo

2017-05-28

We describe the current state of the search for direct, surviving samples of early, inner Solar System fluids-fluid inclusions in meteorites. Meteoritic aqueous fluid inclusions are not rare, but they are very tiny and their characterization is at the state of the art for most analytical techniques. Meteoritic fluid inclusions offer us a unique opportunity to study early Solar System brines in the laboratory. Inclusion-by-inclusion analyses of the trapped fluids in carefully selected samples will, in the immediate future, provide us detailed information on the evolution of fluids as they interacted with anhydrous solid materials. Thus, real data can replace calculated fluid compositions in thermochemical calculations of the evolution of water and aqueous reactions in comets, asteroids, moons and the terrestrial planets.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'. © 2017 The Author(s).

A hydrogen energy carrier. Volume 2: Systems analysis

NASA Technical Reports Server (NTRS)

Savage, R. L. (Editor); Blank, L. (Editor); Cady, T. (Editor); Cox, K. (Editor); Murray, R. (Editor); Williams, R. D. (Editor)

1973-01-01

A systems analysis of hydrogen as an energy carrier in the United States indicated that it is feasible to use hydrogen in all energy use areas, except some types of transportation. These use areas are industrial, residential and commercial, and electric power generation. Saturation concept and conservation concept forecasts of future total energy demands were made. Projected costs of producing hydrogen from coal or from nuclear heat combined with thermochemical decomposition of water are in the range $1.00 to $1.50 per million Btu of hydrogen produced. Other methods are estimated to be more costly. The use of hydrogen as a fuel will require the development of large-scale transmission and storage systems. A pipeline system similar to the existing natural gas pipeline system appears practical, if design factors are included to avoid hydrogen environment embrittlement of pipeline metals. Conclusions from the examination of the safety, legal, environmental, economic, political and societal aspects of hydrogen fuel are that a hydrogen energy carrier system would be compatible with American values and the existing energy system.

Matthew Oliver | NREL

Science.gov Websites

Process Development Unit. NREL's Thermal and Catalytic Process Development Unit can process 1/2 ton per biomass to fuels and chemicals Affiliated Research Programs Thermochemical Process Integration, Scale-Up

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.

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.

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.

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

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.

Aerothermodynamics research at NASA Ames Research Center

NASA Technical Reports Server (NTRS)

Deiwert, George S.

1987-01-01

Research activity in the aerothermodynamics branch at the NASA Ames Research Center is reviewed. Advanced concepts and mission studies relating to the next generation aerospace transportation systems are summarized and directions for continued research identified. Theoretical and computational studies directed at determining flow fields and radiative and convective heating loads in real gases are described. Included are Navier-Stokes codes for equilibrium and thermochemical nonequilibrium air. Experimental studies in the 3.5-ft hypersonic wind tunnel, the ballistic ranges, and the electric arc driven shock tube are described. Tested configurations include generic hypersonic aerospace plane configurations, aeroassisted orbital transfer vehicle shapes and Galileo probe models.

Functional Equivalence Acceptance Testing of FUN3D for Entry Descent and Landing Applications

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Wood, William A.; Kleb, William L.; Alter, Stephen J.; Glass, Christopher E.; Padilla, Jose F.; Hammond, Dana P.; White, Jeffery A.

2013-01-01

The functional equivalence of the unstructured grid code FUN3D to the the structured grid code LAURA (Langley Aerothermodynamic Upwind Relaxation Algorithm) is documented for applications of interest to the Entry, Descent, and Landing (EDL) community. Examples from an existing suite of regression tests are used to demonstrate the functional equivalence, encompassing various thermochemical models and vehicle configurations. Algorithm modifications required for the node-based unstructured grid code (FUN3D) to reproduce functionality of the cell-centered structured code (LAURA) are also documented. Challenges associated with computation on tetrahedral grids versus computation on structured-grid derived hexahedral systems are discussed.

Ceramic Integration Technologies for Advanced Energy Systems: Critical Needs, Technical Challenges, and Opportunities

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay

2010-01-01

Advanced ceramic integration technologies dramatically impact the energy landscape due to wide scale application of ceramics in all aspects of alternative energy production, storage, distribution, conservation, and efficiency. Examples include fuel cells, thermoelectrics, photovoltaics, gas turbine propulsion systems, distribution and transmission systems based on superconductors, nuclear power generation and waste disposal. Ceramic integration technologies play a key role in fabrication and manufacturing of large and complex shaped parts with multifunctional properties. However, the development of robust and reliable integrated systems with optimum performance requires the understanding of many thermochemical and thermomechanical factors, particularly for high temperature applications. In this presentation, various needs, challenges, and opportunities in design, fabrication, and testing of integrated similar (ceramic ceramic) and dissimilar (ceramic metal) material www.nasa.gov 45 ceramic-ceramic-systems have been discussed. Experimental results for bonding and integration of SiC based Micro-Electro-Mechanical-Systems (MEMS) LDI fuel injector and advanced ceramics and composites for gas turbine applications are presented.

Analysis of quasi-hybrid solid rocket booster concepts for advanced earth-to-orbit vehicles

NASA Technical Reports Server (NTRS)

Zurawski, Robert L.; Rapp, Douglas C.

1987-01-01

A study was conducted to assess the feasibility of quasi-hybrid solid rocket boosters for advanced Earth-to-orbit vehicles. Thermochemical calculations were conducted to determine the effect of liquid hydrogen addition, solids composition change plus liquid hydrogen addition, and the addition of an aluminum/liquid hydrogen slurry on the theoretical performance of a PBAN solid propellant rocket. The space shuttle solid rocket booster was used as a reference point. All three quasi-hybrid systems theoretically offer higher specific impulse when compared with the space shuttle solid rocket boosters. However, based on operational and safety considerations, the quasi-hybrid rocket is not a practical choice for near-term Earth-to-orbit booster applications. Safety and technology issues pertinent to quasi-hybrid rocket systems are discussed.

Thermochemically recuperated and steam cooled gas turbine system

DOEpatents

Viscovich, P.W.; Bannister, R.L.

1995-07-11

A gas turbine system is described in which the expanded gas from the turbine section is used to generate the steam in a heat recovery steam generator and to heat a mixture of gaseous hydrocarbon fuel and the steam in a reformer. The reformer converts the hydrocarbon gas to hydrogen and carbon monoxide for combustion in a combustor. A portion of the steam from the heat recovery steam generator is used to cool components, such as the stationary vanes, in the turbine section, thereby superheating the steam. The superheated steam is mixed into the hydrocarbon gas upstream of the reformer, thereby eliminating the need to raise the temperature of the expanded gas discharged from the turbine section in order to achieve effective conversion of the hydrocarbon gas. 4 figs.

Influence of feedstock particle size on lignocellulose conversion--a review.

PubMed

Vidal, Bernardo C; Dien, Bruce S; Ting, K C; Singh, Vijay

2011-08-01

Feedstock particle sizing can impact the economics of cellulosic ethanol commercialization through its effects on conversion yield and energy cost. Past studies demonstrated that particle size influences biomass enzyme digestibility to a limited extent. Physical size reduction was able to increase conversion rates to maximum of ≈ 50%, whereas chemical modification achieved conversions of >70% regardless of biomass particle size. This suggests that (1) mechanical pretreatment by itself is insufficient to attain economically feasible biomass conversion, and, therefore, (2) necessary particle sizing needs to be determined in the context of thermochemical pretreatment employed for lignocellulose conversion. Studies of thermochemical pretreatments that have taken into account particle size as a factor have exhibited a wide range of maximal sizes (i.e., particle sizes below which no increase in pretreatment effectiveness, measured in terms of the enzymatic conversion resulting from the pretreatment, were observed) from <0.15 to 50 mm. Maximal sizes as defined above were dependent on the pretreatment employed, with maximal size range decreasing as follows: steam explosion > liquid hot water > dilute acid and base pretreatments. Maximal sizes also appeared dependent on feedstock, with herbaceous or grassy biomass exhibiting lower maximal size range (<3 mm) than woody biomass (>3 mm). Such trends, considered alongside the intensive energy requirement of size reduction processes, warrant a more systematic study of particle size effects across different pretreatment technologies and feedstock, as a requisite for optimizing the feedstock supply system.

Analytic and experimental evaluation of flowing air test conditions for selected metallics in a shuttle TPS application

NASA Technical Reports Server (NTRS)

Schaefer, J. W.; Tong, H.; Clark, K. J.; Suchsland, K. E.; Neuner, G. J.

1975-01-01

A detailed experimental and analytical evaluation was performed to define the response of TD nickel chromium alloy (20 percent chromium) and coated columbium (R512E on CB-752 and VH-109 on WC129Y) to shuttle orbiter reentry heating. Flight conditions important to the response of these thermal protection system (TPS) materials were calculated, and test conditions appropriate to simulation of these flight conditions in flowing air ground test facilities were defined. The response characteristics of these metallics were then evaluated for the flight and representative ground test conditions by analytical techniques employing appropriate thermochemical and thermal response computer codes and by experimental techniques employing an arc heater flowing air test facility and flat face stagnation point and wedge test models. These results were analyzed to define the ground test requirements to obtain valid TPS response characteristics for application to flight. For both material types in the range of conditions appropriate to the shuttle application, the surface thermochemical response resulted in a small rate of change of mass and a negligible energy contribution. The thermal response in terms of surface temperature was controlled by the net heat flux to the surface; this net flux was influenced significantly by the surface catalycity and surface emissivity. The surface catalycity must be accounted for in defining simulation test conditions so that proper heat flux levels to, and therefore surface temperatures of, the test samples are achieved.

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars.

PubMed

Marcucci, Emma C; Hynek, Brian M

2014-03-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1-60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals.

Laboratory simulations of acid-sulfate weathering under volcanic hydrothermal conditions: Implications for early Mars

PubMed Central

Marcucci, Emma C; Hynek, Brian M

2014-01-01

We have completed laboratory experiments and thermochemical equilibrium models to investigate secondary mineral formation under conditions akin to volcanic, hydrothermal acid-sulfate weathering systems. Our research used the basaltic mineralogy at Cerro Negro Volcano, Nicaragua, characterized by plagioclase, pyroxene, olivine, and volcanic glass. These individual minerals and whole-rock field samples were reacted in the laboratory with 1 molal sulfuric acid at varying temperatures (65, 150, and 200°C), fluid:rock weight ratios (1:1, 4:1, and 10:1), and durations (1–60 days). Thermochemical equilibrium models were developed using Geochemist's Workbench. To understand the reaction products and fluids, we employed scanning electron microscopy/energy dispersive spectroscopy, X-ray diffraction, and inductively coupled plasma-atomic emission spectroscopy. The results of our experiments and models yielded major alteration minerals that include anhydrite, natroalunite, minor iron oxide, and amorphous Al-Si gel. We found that variations in experimental parameters did not drastically change the suite of minerals produced; instead, abundance, size, and crystallographic shape changed. Our results also suggest that it is essential to separate phases formed during experiments from those formed during fluid evaporation to fully understand the reaction processes. Our laboratory reacted and model predicted products are consistent with the mineralogy observed at places on Mars. However, our results indicate that determination of the formation conditions requires microscopic imagery and regional context, as well as a thorough understanding of contributions from both experiment precipitation and fluid evaporation minerals. PMID:26213665

Model predictive control of a solar-thermal reactor

NASA Astrophysics Data System (ADS)

Saade Saade, Maria Elizabeth

Solar-thermal reactors represent a promising alternative to fossil fuels because they can harvest solar energy and transform it into storable and transportable fuels. The operation of solar-thermal reactors is restricted by the available sunlight and its inherently transient behavior, which affects the performance of the reactors and limits their efficiency. Before solar-thermal reactors can become commercially viable, they need to be able to maintain a continuous high-performance operation, even in the presence of passing clouds. A well-designed control system can preserve product quality and maintain stable product compositions, resulting in a more efficient and cost-effective operation, which can ultimately lead to scale-up and commercialization of solar thermochemical technologies. In this work, we propose a model predictive control (MPC) system for a solar-thermal reactor for the steam-gasification of biomass. The proposed controller aims at rejecting the disturbances in solar irradiation caused by the presence of clouds. A first-principles dynamic model of the process was developed. The model was used to study the dynamic responses of the process variables and to identify a linear time-invariant model used in the MPC algorithm. To provide an estimation of the disturbances for the control algorithm, a one-minute-ahead direct normal irradiance (DNI) predictor was developed. The proposed predictor utilizes information obtained through the analysis of sky images, in combination with current atmospheric measurements, to produce the DNI forecast. In the end, a robust controller was designed capable of rejecting disturbances within the operating region. Extensive simulation experiments showed that the controller outperforms a finely-tuned multi-loop feedback control strategy. The results obtained suggest that our controller is suitable for practical implementation.

Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

NASA Astrophysics Data System (ADS)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Johnston, David T.

2018-02-01

Ultramafic-hosted hydrothermal systems - characterized by ongoing serpentinization reactions - exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20‧N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209). In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of -33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (<120 °C) that permitted microbial activity. The change in temperature regime is locally preserved in individual samples and correlates with the progressive uplift and exposure of mantle rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these systems. Overall, the combined application of in situ and bulk rock multiple sulfur isotope measurements with petrographic observations allows us to resolve the different episodes of sulfur cycling during alteration of the oceanic lithosphere and the temporal changes between abiogenic and biogenic processes that control the sulfur cycling in these systems.

A solar-hydrogen economy for U.S.A.

NASA Astrophysics Data System (ADS)

Bockris, J. Om.; Veziroglu, T. N.

The benefits, safety, production, distribution, storage, and uses, as well as the economics of a solar and hydrogen based U.S. energy system are described. Tropical and subtropical locations for the generation plants would provide power from photovoltaics, heliostat arrays, OTEC plants, or genetically engineered algae to produce hydrogen by electrolysis, direct thermal conversion, thermochemical reactions, photolysis, or hybrid systems. Either pipelines for gas transport or supertankers for liquefied hydrogen would distribute the fuel, with storage in underground reservoirs, aquifers, and pressurized bladders at sea. The fuel would be distributed to factories, houses, gas stations, and airports. It can be used in combustion engines, gas turbines, and jet engines, and produces water vapor as an exhaust gas. The necessary research effort to define and initiate construction of technically and economically viable solar-hydrogen plants is projected to be 3 yr, while the technical definition of fusion power plants, the other nondepletable energy system, is expected to take 25 yr.

Materials for engine applications above 3000 deg F: An overview

NASA Technical Reports Server (NTRS)

Shaw, Nancy J.; Dicarlo, James A.; Jacobson, Nathan S.; Levine, Stanley R.; Nesbitt, James A.; Probst, Hubert B.; Sanders, William A.; Stearns, Carl A.

1987-01-01

Materials for future generations of aeropropulsion systems will be required to perform at ever-increasing temperatures and have properties superior to the current state of the art. Improved engine efficiency can reduce specific fuel consumption and thus increase range and reduce operating costs. The ultimate payoff gain is expected to come when materials are developed which can perform without cooling at gas temperatures to 2200 C (4000 F). An overview is presented of materials for applications above 1650 C (3000 F), some pertinent physical property data, and the rationale used: (1) to arrive at recommendations of material systems that qualify for further investigation, and (2) to develop a proposed plan of research. From an analysis of available thermochemical data it was included that such materials systems must be composed of oxide ceramics. The required structural integrity will be achieved by developing these materials into fiber-reinforced ceramic composites.

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.

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

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.

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

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.

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.

Design of an ammonia closed-loop storage system in a CSP power plant with a power tower cavity receiver

NASA Astrophysics Data System (ADS)

Abdiwe, Ramadan; Haider, Markus

2017-06-01

In this study the thermochemical system using ammonia as energy storage carrier is investigated and a transient mathematical model using MATLAB software was developed to predict the behavior of the ammonia closed-loop storage system including but not limited to the ammonia solar reactor and the ammonia synthesis reactor. The MATLAB model contains transient mass and energy balances as well as chemical equilibrium model for each relevant system component. For the importance of the dissociation and formation processes in the system, a Computational Fluid Dynamics (CFD) simulation on the ammonia solar and synthesis reactors has been performed. The CFD commercial package FLUENT is used for the simulation study and all the important mechanisms for packed bed reactors are taken into account, such as momentum, heat and mass transfer, and chemical reactions. The FLUENT simulation reveals the profiles inside both reactors and compared them with the profiles from the MATLAB code.

CHEETAH: A fast thermochemical code for detonation

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

Fried, L.E.

1993-11-01

For more than 20 years, TIGER has been the benchmark thermochemical code in the energetic materials community. TIGER has been widely used because it gives good detonation parameters in a very short period of time. Despite its success, TIGER is beginning to show its age. The program`s chemical equilibrium solver frequently crashes, especially when dealing with many chemical species. It often fails to find the C-J point. Finally, there are many inconveniences for the user stemming from the programs roots in pre-modern FORTRAN. These inconveniences often lead to mistakes in preparing input files and thus erroneous results. We are producingmore » a modern version of TIGER, which combines the best features of the old program with new capabilities, better computational algorithms, and improved packaging. The new code, which will evolve out of TIGER in the next few years, will be called ``CHEETAH.`` Many of the capabilities that will be put into CHEETAH are inspired by the thermochemical code CHEQ. The new capabilities of CHEETAH are: calculate trace levels of chemical compounds for environmental analysis; kinetics capability: CHEETAH will predict chemical compositions as a function of time given individual chemical reaction rates. Initial application: carbon condensation; CHEETAH will incorporate partial reactions; CHEETAH will be based on computer-optimized JCZ3 and BKW parameters. These parameters will be fit to over 20 years of data collected at LLNL. We will run CHEETAH thousands of times to determine the best possible parameter sets; CHEETAH will fit C-J data to JWL`s,and also predict full-wall and half-wall cylinder velocities.« less

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.

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).

Natural Convection Heat Transfer in a Rectangular Liquid Metal Pool With Bottom Heating and Top Cooling

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

Lee, Il S.; Yu, Yong H.; Son, Hyoung M.

2006-07-01

An experimental study is performed to investigate the natural convection heat transfer characteristics with subcooled coolant to create engineering database for basic applications in a lead alloy cooled reactor. Tests are performed in the ALTOS (Applied Liquid-metal Thermal Operation Study) apparatus as part of MITHOS (Metal Integrated Thermo Hydrodynamic Operation System). A relationship is determined between the Nusselt number Nu and the Rayleigh number Ra in the liquid metal rectangular pool. Results are compared with correlations and experimental data in the literature. Given the similar Ra condition, the present test results for Nu of the liquid metal pool with topmore » subcooling are found to be similar to those predicted by the existing correlations or experiments. The current test results are utilized to develop natural convection heat transfer correlations applicable to low Prandtl number Pr fluids that are heated from below and cooled by the external coolant above. Results from this study are slated to be used in designing BORIS (Battery Optimized Reactor Integral System), a small lead cooled modular fast reactor for deployment at remote sites cycled with MOBIS (Modular Optimized Brayton Integral System) for electricity generation, tied with NAVIS (Naval Application Vessel Integral System) for ship propulsion, joined with THAIS (Thermochemical Hydrogen Acquisition Integral System) for hydrogen production, and coupled with DORIS (Desalination Optimized Reactor Integral System) for seawater desalination. Tests are performed with Wood's metal (Pb-Bi-Sn-Cd) filling a rectangular pool whose lower surface is heated and upper surface cooled by forced convection of water. The test section is 20 cm long, 11.3 cm high and 15 cm wide. The simulant has a melting temperature of 78 deg. C. The constant temperature and heat flux condition was realized for the bottom heating once the steady state had been met. The test parameters include the heated bottom surface temperature of the liquid metal pool, the input power to the bottom surface of the section, and the coolant temperature. (authors)« less

The MgO-Al2O3-SiO2 system - Free energy of pyrope and Al2O3-enstatite. [in earth mantle formation

NASA Technical Reports Server (NTRS)

Saxena, S. K.

1981-01-01

The model of fictive ideal components is used to determine Gibbs free energies of formation of pyrope and Al2O3-enstatite from the experimental data on coexisting garnet and orthopyroxene and orthopyroxene and spinel in the temperature range 1200-1600 K. It is noted that Al2O3 forms an ideal solution with MgSiO3. These thermochemical data are found to be consistent with the Al2O3 isopleths that could be drawn using most recent experimental data and with the reversed experimental data on the garnet-spinel field boundary.

Reliability Estimating Procedures for Electric and Thermochemical Propulsion Systems. Volume 1

DTIC Science & Technology

1977-02-01

Laboratories, The Marquardt Company, NASA Goddard Space Flight Center, RCA Astro Elec- tronics, Rockwell International, Applied Physics Laboratory...E fX ) 2.3 Failure Rate Means and Bounds 5% Lower Bound Median Mean 95% Upper Bound A.05 X.05 . AIA. 9 5 0.00025 0.0024 0.06 0.022 x10- 6 per cycle, 1...Iq IIt. Xg4 4l Wl ~ 4𔃺 L Q ൘ I1-269 I- I J N1- 74-i Liu I- (~J~~~jto 1-27 r4J > U 0 1-271 T 27 fX ~𔃽 0L 1-273 -- va VAv( 13 1-272 %J% ~ii 000 41

Applications of Electromagnetic Levitation and Development of Mathematical Models: A Review of the Last 15 Years (2000 to 2015)

NASA Astrophysics Data System (ADS)

Gao, Lei; Shi, Zhe; Li, Donghui; Zhang, Guifang; Yang, Yindong; McLean, Alexander; Chattopadhyay, Kinnor

2016-02-01

Electromagnetic levitation (EML) is a contact-less, high-temperature technique which has had extensive application with respect to the investigation of both thermophysical and thermochemical properties of liquid alloy systems. The varying magnetic field generates an induced current inside the metal droplet, and interactions are created which produce both the Lorentz force that provides support against gravity and the Joule heating effect that melts the levitated specimen. Since metal droplets are opaque, transport phenomena inside the droplet cannot be visualized. To address this aspect, several numerical modeling techniques have been developed. The present work reviews the applications of EML techniques as well as the contributions that have been made by the use of mathematical modeling to improve understanding of the inherent processes which are characteristic features of the levitation system.

Use of ceramics in point-focus solar receivers

NASA Technical Reports Server (NTRS)

Smoak, R. H.; Kudirka, A. A.

1981-01-01

One of the research and development efforts in the Solar Thermal Energy Systems Project at the Jet Propulsion Laboratory has been focused on application of ceramic components for advanced point-focus solar receivers. The impetus for this effort is a need for high efficiency, low cost solar receivers which operate in a temperature regime where use of metal components is impractical. The current status of the work on evaluation of ceramic components at JPL and elsewhere is outlined and areas where lack of knowledge is currently slowing application of ceramics are discussed. Future developments of ceramic processing technology and reliability assurance methodology should open up applications for the point-focus solar concentrator system in fuels and chemicals production, in thermochemical energy transport and storage, in detoxification of hazardous materials and in high temperature process heat as well as for electric power generation.

Tungsten - Yttrium Based Nuclear Structural Materials

NASA Astrophysics Data System (ADS)

Ramana, Chintalapalle; Chessa, Jack; Martinenz, Gustavo

2013-04-01

The challenging problem currently facing the nuclear science community in this 21st century is design and development of novel structural materials, which will have an impact on the next-generation nuclear reactors. The materials available at present include reduced activation ferritic/martensitic steels, dispersion strengthened reduced activation ferritic steels, and vanadium- or tungsten-based alloys. These materials exhibit one or more specific problems, which are either intrinsic or caused by reactors. This work is focussed towards tungsten-yttrium (W-Y) based alloys and oxide ceramics, which can be utilized in nuclear applications. The goal is to derive a fundamental scientific understanding of W-Y-based materials. In collaboration with University of Califonia -- Davis, the project is designated to demonstrate the W-Y based alloys, ceramics and composites with enhanced physical, mechanical, thermo-chemical properties and higher radiation resistance. Efforts are focussed on understanding the microstructure, manipulating materials behavior under charged-particle and neutron irradiation, and create a knowledge database of defects, elemental diffusion/segregation, and defect trapping along grain boundaries and interfaces. Preliminary results will be discussed.

Combustor kinetic energy efficiency analysis of the hypersonic research engine data

NASA Astrophysics Data System (ADS)

Hoose, K. V.

1993-11-01

A one-dimensional method for measuring combustor performance is needed to facilitate design and development scramjet engines. A one-dimensional kinetic energy efficiency method is used for measuring inlet and nozzle performance. The objective of this investigation was to assess the use of kinetic energy efficiency as an indicator for scramjet combustor performance. A combustor kinetic energy efficiency analysis was performed on the Hypersonic Research Engine (HRE) data. The HRE data was chosen for this analysis due to its thorough documentation and availability. The combustor, inlet, and nozzle kinetic energy efficiency values were utilized to determine an overall engine kinetic energy efficiency. Finally, a kinetic energy effectiveness method was developed to eliminate thermochemical losses from the combustion of fuel and air. All calculated values exhibit consistency over the flight speed range. Effects from fuel injection, altitude, angle of attack, subsonic-supersonic combustion transition, and inlet spike position are shown and discussed. The results of analyzing the HRE data indicate that the kinetic energy efficiency method is effective as a measure of scramjet combustor performance.

New insights into meat by-product utilization.

PubMed

Toldrá, Fidel; Mora, Leticia; Reig, Milagro

2016-10-01

Meat industry generates large volumes of by-products like blood, bones, meat trimmings, skin, fatty tissues, horns, hoofs, feet, skull and viscera among others that are costly to be treated and disposed ecologically. These costs can be balanced through innovation to generate added value products that increase its profitability. Rendering results in feed ingredients for livestock, poultry and aquaculture as well as for pet foods. Energy valorization can be obtained through the thermochemical processing of meat and bone meal or the use of waste animal fats for the production of biodiesel. More recently, new applications have been reported like the production of polyhydroxyalkanoates as alternative to plastics produced from petroleum. Other interesting valorization strategies are based on the hydrolysis of by-products to obtain added value products like bioactive peptides with relevant physiological effects as antihypertensive, antioxidant, antidiabetic, antimicrobial, etc. with promising applications in the food, pharmaceutical and cosmetics industry. This paper reports and discusses the latest developments and trends in the use and valorisation of meat industry by-products. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

Thermochemical cycles for the production of hydrogen

DOEpatents

Steinberg, M.; Dang, V.D.

Two-step processes for the preparation of hydrogen are described: CrCl/sub 3/(g) ..-->.. CrCl/sub 2/(g) + 1/2Cl/sub 2/(g) and CrCl/sub 2/(s) + HCl(g) reversible CrCl/sub 3/(s) + 1/2H/sub 2/(g); UCl/sub 4/(g) ..-->.. UCl/sub 3/(g) + 1/2Cl/sub 2/(g) and UCl/sub 3/(s) + HCl(g) ..-->.. UCl/sub 4/(s) + 1/2H/sub 2/(g); and CaSO/sub 4/(s) ..-->.. CaO(s) + SO/sub 2/(g) + 1/2O/sub 2/(g) and CaO(s) + SO/sub 2/(g) + H/sub 2/O(l) ..-->.. CaSO/sub 4/(s) + H/sub 2/(g). The high temperature available from solar collectors, high temperature gas reactors or fusion reactors is utilized in the first step in which the reaction is endothermic. The efficiency is at least 60% and with process heat recovery, the efficiency may be increased up to 74.4%. An apparatus fr carrying out the process in conjunction with a fusion reactor, is described.

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

Stechel, Ellen Beth; Ambrosini, Andrea; Coker, Eric Nicholas

The Sunshine to Petrol effort at Sandia aims to convert carbon dioxide and water to precursors for liquid hydrocarbon fuels using concentrated solar power. Significant advances have been made in the field of solar thermochemical CO{sub 2}-splitting technologies utilizing yttria-stabilized zirconia (YSZ)-supported ferrite composites. Conceptually, such materials work via the basic redox reactions: Fe{sub 3}O{sub 4} {yields} 3FeO + 0.5O{sub 2} (Thermal reduction, >1350 C) and 3FeO + CO{sub 2} {yields} Fe{sub 3}O{sub 4} + CO (CO{sub 2}-splitting oxidation, <1200 C). There has been limited fundamental characterization of the ferrite-based materials at the high temperatures and conditions present in thesemore » cycles. A systematic study of these composites is underway in an effort to begin to elucidate microstructure, structure-property relationships, and the role of the support on redox behavior under high-temperature reducing and oxidizing environments. In this paper the synthesis, structural characterization (including scanning electron microscopy and room temperature and in-situ x-ray diffraction), and thermogravimetric analysis of YSZ-supported ferrites will be reported.« less

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...

Evaluation of biochars by temperature programmed oxidation/mass spectroscopy

USDA-ARS?s Scientific Manuscript database

Biochar from the thermochemical conversion of biomass was evaluated by Temperature Programmed Oxidation (TPO) coupled with mass spectroscopy. This technique can be used to assess the oxidative reactivity of carbonaceous solids where higher temperature reactivity indicates greater structural order. ...

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...

Mission and Programs | NREL

Science.gov Websites

Government International, Research, and Nonprofit Organizations R&D Programs NREL is the only federal laboratory dedicated to the research, development, commercialization, and deployment of renewable energy and Program supports NREL research and development that focuses on biomass characterization, thermochemical

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...

The complexities of hydrolytic enzymes from the termite digestive system.

PubMed

Saadeddin, Anas

2014-06-01

The main challenge in second generation bioethanol production is the efficient breakdown of cellulose to sugar monomers (hydrolysis). Due to the recalcitrant character of cellulose, feedstock pretreatment and adapted hydrolysis steps are needed to obtain fermentable sugar monomers. The conventional industrial production process of second-generation bioethanol from biomass comprises several steps: thermochemical pretreatment, enzymatic hydrolysis and sugar fermentation. This process is undergoing continuous optimization in order to increase the bioethanol yield and reduce the economic cost. Therefore, the discovery of new enzymes with high lignocellulytic activity or new strategies is extremely important. In nature, wood-feeding termites have developed a sophisticated and efficient cellulose degrading system in terms of the rate and extent of cellulose hydrolysis and exploitation. This system, which represents a model for digestive symbiosis has attracted the attention of biofuel researchers. This review describes the termite digestive system, gut symbionts, termite enzyme resources, in vitro studies of isolated enzymes and lignin degradation in termites.

Toward large-scale solar energy systems with peak concentrations of 20,000 suns

NASA Astrophysics Data System (ADS)

Kribus, Abraham

1997-10-01

The heliostat field plays a crucial role in defining the achievable limits for central receiver system efficiency and cost. Increasing system efficiency, thus reducing the reflective area and system cost, can be achieved by increasing the concentration and the receiver temperature. The concentration achievable in central receiver plants, however, is constrained by current heliostat technology and design practices. The factors affecting field performance are surface and tracking errors, astigmatism, shadowing, blocking and dilution. These are geometric factors that can be systematically treated and reduced. We present improvements in collection optics and technology that may boost concentration (up to 20,000 peak), achievable temperature (2,000 K), and efficiency in solar central receiver plants. The increased performance may significantly reduce the cost of solar energy in existing applications, and enable solar access to new ultra-high-temperature applications, such as: future gas turbines approaching 60% combined cycle efficiency; high-temperature thermo-chemical processes; and gas-dynamic processes.

The potential impacts of biomass feedstock production on water resource availability.

PubMed

Stone, K C; Hunt, P G; Cantrell, K B; Ro, K S

2010-03-01

Biofuels are a major topic of global interest and technology development. Whereas bioenergy crop production is highly dependent on water, bioenergy development requires effective allocation and management of water. The objectives of this investigation were to assess the bioenergy production relative to the impacts on water resource related factors: (1) climate and weather impact on water supplies for biomass production; (2) water use for major bioenergy crop production; and (3) potential alternatives to improve water supplies for bioenergy. Shifts to alternative bioenergy crops with greater water demand may produce unintended consequences for both water resources and energy feedstocks. Sugarcane and corn require 458 and 2036 m(3) water/m(3) ethanol produced, respectively. The water requirements for corn grain production to meet the US-DOE Billion-Ton Vision may increase approximately 6-fold from 8.6 to 50.1 km(3). Furthermore, climate change is impacting water resources throughout the world. In the western US, runoff from snowmelt is occurring earlier altering the timing of water availability. Weather extremes, both drought and flooding, have occurred more frequently over the last 30 years than the previous 100 years. All of these weather events impact bioenergy crop production. These events may be partially mitigated by alternative water management systems that offer potential for more effective water use and conservation. A few potential alternatives include controlled drainage and new next-generation livestock waste treatment systems. Controlled drainage can increase water available to plants and simultaneously improve water quality. New livestock waste treatments systems offer the potential to utilize treated wastewater to produce bioenergy crops. New technologies for cellulosic biomass conversion via thermochemical conversion offer the potential for using more diverse feedstocks with dramatically reduced water requirements. The development of bioenergy feedstocks in the US and throughout the world should carefully consider water resource limitations and their critical connections to ecosystem integrity and sustainability of human food. Published by Elsevier Ltd.

Ceramic Integration Technologies for Aerospace and Energy Systems: Technical Challenges and Opportunities

NASA Technical Reports Server (NTRS)

Singh, Mrityunjay

2007-01-01

Ceramic integration technology has been recognized as an enabling technology for the implementation of advanced ceramic systems in a number of high-temperature applications in aerospace, power generation, nuclear, chemical, and electronic industries. Various ceramic integration technologies (joining, brazing, attachments, repair, etc.) play a role in fabrication and manufacturing of large and complex shaped parts of various functionalities. However, the development of robust and reliable integrated systems with optimum performance requires the understanding of many thermochemical and thermomechanical factors, particularly for high temperature applications. In this presentation, various challenges and opportunities in design, fabrication, and testing of integrated similar (ceramic-ceramic) and dissimilar (ceramic-metal) material systems will be discussed. Experimental results for bonding and integration of SiC based LDI fuel injector, high conductivity C/C composite based heat rejection system, solid oxide fuel cells system, ultra high temperature ceramics for leading edges, and ceramic composites for thermostructural applications will be presented. Potential opportunities and need for the development of innovative design philosophies, approaches, and integrated system testing under simulated application conditions will also be discussed.

MODEL BASED BIOMASS SYSTEM DESIGN OF FEEDSTOCK SUPPLY SYSTEMS FOR BIOENERGY PRODUCTION

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

David J. Muth, Jr.; Jacob J. Jacobson; Kenneth M. Bryden

Engineering feedstock supply systems that deliver affordable, high-quality biomass remains a challenge for the emerging bioenergy industry. Cellulosic biomass is geographically distributed and has diverse physical and chemical properties. Because of this feedstock supply systems that deliver cellulosic biomass resources to biorefineries require integration of a broad set of engineered unit operations. These unit operations include harvest and collection, storage, preprocessing, and transportation processes. Design decisions for each feedstock supply system unit operation impact the engineering design and performance of the other system elements. These interdependencies are further complicated by spatial and temporal variances such as climate conditions and biomassmore » characteristics. This paper develops an integrated model that couples a SQL-based data management engine and systems dynamics models to design and evaluate biomass feedstock supply systems. The integrated model, called the Biomass Logistics Model (BLM), includes a suite of databases that provide 1) engineering performance data for hundreds of equipment systems, 2) spatially explicit labor cost datasets, and 3) local tax and regulation data. The BLM analytic engine is built in the systems dynamics software package PowersimTM. The BLM is designed to work with thermochemical and biochemical based biofuel conversion platforms and accommodates a range of cellulosic biomass types (i.e., herbaceous residues, short- rotation woody and herbaceous energy crops, woody residues, algae, etc.). The BLM simulates the flow of biomass through the entire supply chain, tracking changes in feedstock characteristics (i.e., moisture content, dry matter, ash content, and dry bulk density) as influenced by the various operations in the supply chain. By accounting for all of the equipment that comes into contact with biomass from the point of harvest to the throat of the conversion facility and the change in characteristics, the BLM evaluates economic performance of the engineered system, as well as determining energy consumption and green house gas performance of the design. This paper presents a BLM case study delivering corn stover to produce cellulosic ethanol. The case study utilizes the BLM to model the performance of several feedstock supply system designs. The case study also explores the impact of temporal variations in climate conditions to test the sensitivity of the engineering designs. Results from the case study show that under certain conditions corn stover can be delivered to the cellulosic ethanol biorefinery for $35/dry ton.« less

Chemsheet as a Simulation Platform for Pyrometallurgical Processes

NASA Astrophysics Data System (ADS)

Penttilä, Karri; Salminen, Justin; Tripathi, Nagendra; Koukkari, Pertti

ChemSheet is a thermodynamic multi-phase multi-component simulation software, which is used as an Add-in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off-line modeling of Cu-flash smelters and advanced thermochemical simulation coupled with on-line process control of Cu-Ni smelting. The presentation will describe an off-line model of Cu-smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si -system (slag, matte and liquid metal) by using the quasichemical model. A four-stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on-line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid-bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.