Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

Directory of Open Access Journals (Sweden)

Rahul Bhosale

2016-01-01

Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

Nuclear Production of Hydrogen Using Thermochemical Water-Splitting Cycles

International Nuclear Information System (INIS)

Brown, L.C.; Besenbruch, G.E.; Schultz, K.R.; Marshall, A.C.; Showalter, S.K.; Pickard, P.S.; Funk, J.F.

2002-01-01

The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high-temperature heat from an advanced nuclear power station in a thermochemical water-splitting cycle. We carried out a detailed literature search to create a searchable database with 115 cycles and 822 references. We developed screening criteria to reduce the list to 25 cycles. We used detailed evaluation to select two cycles that appear most promising, the Adiabatic UT-3 cycle and the Sulfur-Iodine cycle. We have selected the Sulfur-Iodine thermochemical water-splitting cycle for further development. We then assessed the suitability of various nuclear reactor types to the production of hydrogen from water using the Sulfur-Iodine cycle. A basic requirement is to deliver heat to the process interface heat exchanger at temperatures up to 900 deg. C. We considered nine categories of reactors: pressurized water-cooled, boiling water-cooled, organic-cooled, alkali metal-cooled, heavy metal-cooled, gas-cooled, molten salt-cooled, liquid-core and gas-core reactors. We developed requirements and criteria to carry out the assessment, considering design, safety, operational, economic and development issues. This assessment process led to our choice of the helium gas-cooled reactor for coupling to the Sulfur-Iodine cycle. In continuing work, we are investigating the improvements that have been proposed to the Sulfur-Iodine cycle and will generate an integrated flowsheet describing a hydrogen production plant powered by a high-temperature helium gas-cooled nuclear reactor. This will allow us to size process equipment and calculate hydrogen production efficiency and capital cost, and to estimate the cost of the hydrogen produced as a function of nuclear reactor cost. (authors)

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

Science.gov (United States)

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

Hydrogen Production From Water By Thermo-Chemical Methods (UT-3): Evaluation of Side Reactions By Simulation Process

International Nuclear Information System (INIS)

Rusli, A.

1997-01-01

Hydogen fuel with its advantages will be able to replace all the positions of fossil fuels post o il and gas or migas . Among the advantages of hydrogen fuel are pollution free, abundant of raw material in the form of water molecule, flexible in application, able to stroge and transport as well as fossil energy sources (oil and gas). Hydogen could be produced from water by means of thermochemical, thermolysis, photolysis and electrolysis. Nuclear heat (HTGR), solar heat or waste heat from steel industry can be used as energy source for these processes. In case of thermochemical method, some problems realated to production process should be studied and evaluated. Simulation is considered can be applied to study the effects of side reactions and also to resolve its problems in hydrogen production process. In this paper is reported the evalution results of hydrogen production process by thermochemical (UT-3) through both of the experimental and computer simulation. It has been proposed a new flow chart of hydrogen production to achieve the hydrogen production continuously. A simulator has been developed based on experimental data and related mathematical equations. This simulator can be used to scle-up the UT-3 thermochemical cycle for hydrogen production process

Thermochemical water-splitting cycle, bench-scale investigations and process engineering. Annual report, October 1, 1978-September 30, 1979

Energy Technology Data Exchange (ETDEWEB)

Caprioglio, G.; McCorkle, K.H.; Besenbruch, G.E.; Rode, J.S.

1980-03-01

A program to investigate thermochemical water splitting has been under way at General Atomic Company (GA) since October 1972. This document is an annual progress report of Department of Energy (DOE) sponsored process development work on the GA sulfur-iodine thermochemical water splitting cycle. The work consisted of laboratory bench-scale investigations, demonstration of the process in a closed-loop cycle demonstrator, and process engineering design studies. A bench-scale system, consisting of three subunits, has been designed to study the cycle under continuous flow conditions. The designs of subunit I, which models the main solution reaction and product separation, and subunit II, which models the concentration and decomposition of sulfuric acid, were presented in an earlier annual report. The design of subunit III, which models the purification and decomposition of hydrogen iodide, is given in this report. Progress on the installation and operation of subunits I and II is described. A closed-loop cycle demonstrator was installed and operated based on a DOE request. Operation of the GA sulfur-iodine cycle was demonstrated in this system under recycle conditions. The process engineering addresses the flowsheet design of a large-scale production process consisting of four chemical sections (I through IV) and one helium heat supply section (V). The completed designs for sections I through V are presented. The thermal efficiency of the process calculated from the present flowsheet is 47%.

Solar Hydrogen Production via a Samarium Oxide-Based Thermochemical Water Splitting Cycle

Directory of Open Access Journals (Sweden)

Rahul Bhosale

2016-04-01

Full Text Available The computational thermodynamic analysis of a samarium oxide-based two-step solar thermochemical water splitting cycle is reported. The analysis is performed using HSC chemistry software and databases. The first (solar-based step drives the thermal reduction of Sm2O3 into Sm and O2. The second (non-solar step corresponds to the production of H2 via a water splitting reaction and the oxidation of Sm to Sm2O3. The equilibrium thermodynamic compositions related to the thermal reduction and water splitting steps are determined. The effect of oxygen partial pressure in the inert flushing gas on the thermal reduction temperature (TH is examined. An analysis based on the second law of thermodynamics is performed to determine the cycle efficiency (ηcycle and solar-to-fuel energy conversion efficiency (ηsolar−to−fuel attainable with and without heat recuperation. The results indicate that ηcycle and ηsolar−to−fuel both increase with decreasing TH, due to the reduction in oxygen partial pressure in the inert flushing gas. Furthermore, the recuperation of heat for the operation of the cycle significantly improves the solar reactor efficiency. For instance, in the case where TH = 2280 K, ηcycle = 24.4% and ηsolar−to−fuel = 29.5% (without heat recuperation, while ηcycle = 31.3% and ηsolar−to−fuel = 37.8% (with 40% heat recuperation.

Cascading pressure reactor and method for solar-thermochemical reactions

Science.gov (United States)

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.

Probing cycle stability and reversibility in thermochemical energy storage – CaC_2O_4·H_2O as perfect match?

International Nuclear Information System (INIS)

Knoll, Christian; Müller, Danny; Artner, Werner; Welch, Jan M.; Werner, Andreas; Harasek, Michael; Weinberger, Peter

2017-01-01

Highlights: • CaC_2O_4·H_2O dehydration is fully reversible between 25 °C and 200 °C. • Isothermal cycling between hydrate and anhydrate phase can be triggered by the water vapour concentration. • High reaction rates and full reversibility demonstrated over 100 cycles. • Material shows no ageing effects or reactivity decrease. - Abstract: The dehydration and subsequent rehydration of calcium oxalate monohydrate has yet to find application in thermochemical energy storage. Unlike for many other salt hydrates, complete reversibility of the dehydration-rehydration reaction was observed. Additionally, it was found that the rehydration temperature is strongly affected by the water vapour concentration: Full reversibility is not only achieved at room-temperature, but, depending on the water vapour concentration, at up to 200 °C. This allows isothermal switching of the material between charging and discharging by a change of the H_2O-partial pressure. Cycle stability of the material was tested by a long-term stress experiment involving 100 charging and discharging cycles. No signs of material fatigue or reactivity loss were found. In-situ powder X-ray diffraction showed complete rehydration of the material within 300 s. The experimental findings indicate that the CaC_2O_4·H_2O/CaC_2O_4 system is perfectly suited for technical application as a thermochemical energy storage medium.

Thermodynamic analysis of the use a chemical heat pump to link a supercritical water-cooled nuclear reactor and a thermochemical water-splitting cycle for hydrogen production

International Nuclear Information System (INIS)

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

2008-01-01

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

Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power

International Nuclear Information System (INIS)

Brown, L.C.; Funk, J.F.; Showalter, S.K.

1999-01-01

OAK B188 Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power There is currently no large scale, cost-effective, environmentally attractive hydrogen production process, nor is such a process available for commercialization. Hydrogen is a promising energy carrier, which potentially could replace the fossil fuels used in the transportation sector of our economy. Fossil fuels are polluting and carbon dioxide emissions from their combustion are thought to be responsible for global warming. The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high temperature heat from an advanced nuclear power station. Almost 800 literature references were located which pertain to thermochemical production of hydrogen from water and over 100 thermochemical watersplitting cycles were examined. Using defined criteria and quantifiable metrics, 25 cycles have been selected for more detailed study

Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

International Nuclear Information System (INIS)

Werner, R.W.; Ribe, F.L.

1981-01-01

This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units

Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

Energy Technology Data Exchange (ETDEWEB)

Werner, R.W.; Ribe, F.L.

1981-01-21

This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units. (MOW)

Experimental study of a thermochemical compressor for an absorption/compression hybrid cycle

International Nuclear Information System (INIS)

Ventas, R.; Vereda, C.; Lecuona, A.; Venegas, M.

2012-01-01

Highlights: ► Experimental study of a thermochemical compressor for absorption/compression cycle. ► Spray adiabatic absorber using NH 3 –LiNO 3 solution working fluid. ► It is able to operate between 57 and 110 °C varying concentration between 0.46 and 0.59. ► The increase of absorber pressure decreases the circulation ratio. ► The numerical model performed agrees with the experimental results. -- Abstract: An experimental study of a thermochemical compressor with ammonia–lithium nitrate solution as working fluid has been carried out. This compressor incorporates a single-pass adiabatic absorber and all the heat exchangers are of the plate type: absorber subcooler, generator and solution heat exchanger. The thermochemical compressor has been studied as part of a single-effect absorption chiller hybridized with an in-series low-pressure compression booster. The adiabatic absorber uses fog jet injectors. The generator hot water temperatures for the external driving flow are in the range of 57–110 °C and the absorber pressures range between 429 and 945 kPa. Experimental results are compared with a numerical model showing a high agreement. The performance of the thermochemical compressor, evaluated through the circulation ratio, improves for higher absorber pressures, indicating the potential of pressure boosting. For the same circulation ratio, the driving hot water inlet temperature decreases with the rise of the absorber pressure. The thermochemical compressor, based on an adiabatic absorber, can produce refrigerant with very low driving temperatures, between 57 and 70 °C, what is interesting for solar cooling applications and very low temperature residual heat recovery. Efficiencies and cooling power are offered when this hybrid thermochemical compressor is implemented in a chiller, showing the effect of different operating parameters.

Laser thermal effect on silicon nitride ceramic based on thermo-chemical reaction with temperature-dependent thermo-physical parameters

International Nuclear Information System (INIS)

Pan, A.F.; Wang, W.J.; Mei, X.S.; Wang, K.D.; Zhao, W.Q.; Li, T.Q.

2016-01-01

Highlights: • A two-dimensional thermo-chemical reaction model is creatively built. • Thermal conductivity and heat capacity of β-Si_3N_4 are computed accurately. • The appropriate thermo-chemical reaction rate is fitted and reaction element length is set to assure the constringency. • The deepest ablated position was not the center of the ablated area due to plasma absorption. • The simulation results demonstrate the thermo-chemical process cant be simplified to be physical phase transition. - Abstract: In this study, a two-dimensional thermo-chemical reaction model with temperature-dependent thermo-physical parameters on Si_3N_4 with 10 ns laser was developed to investigate the ablated size, volume and surface morphology after single pulse. For model parameters, thermal conductivity and heat capacity of β-Si_3N_4 were obtained from first-principles calculations. Thermal-chemical reaction rate was fitted by collision theory, and then, reaction element length was deduced using the relationship between reaction rate and temperature distribution. Furthermore, plasma absorption related to energy loss was approximated as a function of electron concentration in Si_3N_4. It turned out that theoretical ablated volume and radius increased and then remained constant with increasing laser energy, and the maximum ablated depth was not in the center of the ablated zone. Moreover, the surface maximum temperature of Si_3N_4 was verified to be above 3000 K within pulse duration, and it was much higher than its thermal decomposition temperature of 1800 K, which indicated that Si_3N_4 was not ablated directly above the thermal decomposition temperature. Meanwhile, the single pulse ablation of Si_3N_4 was performed at different powers using a TEM_0_0 10 ns pulse Nd:YAG laser to validate the model. The model showed a satisfactory consistence between the experimental data and numerical predictions, presenting a new modeling technology that may significantly increase the

Design and reliability assessment of control systems for a nuclear-based hydrogen production plant with copper-chlorine thermochemical cycle

Energy Technology Data Exchange (ETDEWEB)

Al-Dabbagh, Ahmad W. [Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario, L1H 7K4 (Canada); Lu, Lixuan [Faculty of Energy Systems and Nuclear Science, Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario, L1H 7K4 (Canada)

2010-02-15

The thermochemical Copper-Chlorine (Cu-Cl) cycle is an emerging new method of nuclear-based hydrogen production. In the process, water is decomposed into hydrogen and oxygen through several physical and chemical processes. In this paper, a Distributed Control System (DCS) is designed for the thermochemical Cu-Cl cycle. The architecture and the communication networks of the DCS are discussed. Reliability of the DCS is assessed using fault trees. In the assessment, the impact of the malfunction of the actuators, sensors, controllers and communication networks on the overall system reliability is investigated. This provides key information for the selection of control system components, and determination of their inspection frequency and maintenance strategy. The hydrogen reactor unit, which is one of the major components in the thermochemical Cu-Cl cycle, is used to demonstrate the detailed design and analysis. (author)

Bimetallic catalysts for HI decomposition in the iodine-sulfur thermochemical cycle

International Nuclear Information System (INIS)

Wang Laijun; Hu Songzhi; Xu Lufei; Li Daocai; Han Qi; Chen Songzhe; Zhang Ping; Xu Jingming

2014-01-01

Among the different kinds of thermochemical water-splitting cycles, the iodine-sulfur (IS) cycle has attracted more and more interest because it is one of the promising candidates for economical and massive hydrogen production. However, there still exist some science and technical problems to be solved before industrialization of the IS process. One such problem is the catalytic decomposition of hydrogen iodide. Although the active carbon supported platinum has been verified to present the excellent performance for HI decomposition, it is very expensive and easy to agglomerate under the harsh condition. In order to decrease the cost and increase the stability of the catalysts for HI decomposition, a series of bimetallic catalysts were prepared and studied at INET. This paper summarized our present research advances on the bimetallic catalysts (Pt-Pd, Pd-Ir and Pt-Ir) for HI decomposition. In the course of the study, the physical properties, structure, and morphology of the catalysts were characterized by specific surface area, X-ray diffractometer; and transmission electron microscopy, respectively. The catalytic activity for HI decomposition was investigated in a fixed bed reactor under atmospheric pressure. The results show that due to the higher activity and better stability, the active carbon supported bimetallic catalyst is more potential candidate than mono metallic Pt catalyst for HI decomposition in the IS thermochemical cycle. (author)

Thermal integration of SCWR nuclear and thermochemical hydrogen plants

International Nuclear Information System (INIS)

Wang, Z.; Naterer, G.F.; Gabriel, K.S.

2010-01-01

In this paper, the intermediate heat exchange between a Generation IV supercritical water-cooled nuclear reactor (SCWR) and a thermochemical hydrogen production cycle is discussed. It is found that the maximum and range of temperatures of a thermochemical cycle are the dominant parameters that affect the design of its coupling with SCWR. The copper-chlorine (Cu-Cl) thermochemical cycle is a promising cycle that can link with SCWRs. The location of extracting heat from a SCWR to a thermochemical cycle is investigated in this paper. Steam bypass lines downstream of the SCWR core are suggested for supplying heat to the Cu-Cl hydrogen production cycle. The stream extraction location is strongly dependent on the temperature requirements of the chemical steps of the thermochemical cycle. The available quantity of heat exchange at different hours of a day is also studied. It is found that the available heat at most hours of power demand in a day can support an industrial scale steam methane reforming plant if the SCWR power station is operating at full design capacity. (author)

Thermochemical recuperative combined cycle with methane-steam reforming combustion; Tennengasu kaishitsu nensho ni yoru konbaindo saikuru hatsuden no kokoritsuka oyobi denryoku fuka heijunka taio

Energy Technology Data Exchange (ETDEWEB)

Kikuchi, R.; Essaki, K.; Tsutsumi, A. [The University of Tokyo, Tokyo (Japan). Dept. of Chemical System Engineering; Kaganoi, S.; Kurimura, H. [Teikoku Sekiyu Co., Tokyo (Japan); Sasaki, T.; Ogawa, T. [Toshiba Co., Tokyo (Japan)

2000-03-10

Thermochemical recuperative combined cycles with methane-steam reforming are proposed for improving their thermal efficiency and for peak-load leveling. For targeting higher thermal efficiency, a cycle with methane-steam reforming reaction heated by gas turbine exhaust was analyzed. The inlet temperature of gas turbine was set at 1,350 degree C. Low-pressure steam extracted from a steam turbine is mixed with methane, and then this mixture is heated by part of the gas turbine exhaust to promote a reforming reaction. The rest of the exhaust heat is used to produce steam, which drives steam turbines to generate electricity. The effect of steam-to-methane ratio (S/C) on thermal efficiency of the cycle, as well as on methane conversion, is investigated by using the ASPEN Plus process simulator. The methane feed rate was fixed at constant and S/C ratio was varied from 2.25 to 4.75. Methane conversion shows an increasing trend toward the ratio and has a maximum value of 17.9 % at S/C=4.0. Thermal efficiency for the system is about 51 % higher than that calculated for a conventional 1,300 degree C class combined cycle under similar conditions. A thermochemical recuperative combined cycle is designed for peak-load leveling. In night-time operation from 20 : 00 to 8 : 00 it stores hydrogen produced by methane steam reforming at S/C=3.9 to save power generation. The gas turbine inlet temperature is 1,330 degree C. In daytime operation from 8 : 00 to 20 : 00 the chemically recuperated combined cycle operated at S/C=2.0 is driven by the mixture of a combined cycle operated at constant load with the same methane feed rate, whereas daytime operation generated power 1.26 times larger than that of the combined cycle. (author)

Hydrogen production system based on high temperature gas cooled reactor energy using the sulfur-iodine (SI) thermochemical water splitting cycle

International Nuclear Information System (INIS)

Garcia, L.; Gonzalez, D.

2011-01-01

Hydrogen production from water using nuclear energy offers one of the most attractive zero-emission energy strategies and the only one that is practical on a substantial scale. Recently, strong interest is seen in hydrogen production using heat of a high-temperature gas-cooled reactor. The high-temperature characteristics of the modular helium reactor (MHR) make it a strong candidate for producing hydrogen using thermochemical or high-temperature electrolysis (HTE) processes. Eventually it could be also employ a high-temperature gas-cooled reactor (HTGR), which is particularly attractive because it has unique capability, among potential future generation nuclear power options, to produce high-temperature heat ideally suited for nuclear-heated hydrogen production. Using heat from nuclear reactors to drive a sulfur-iodine (SI) thermochemical hydrogen production process has been interest of many laboratories in the world. One of the promising approaches to produce large quantity of hydrogen in an efficient way using the nuclear energy is the sulfur-iodine (SI) thermochemical water splitting cycle. Among the thermochemical cycles, the sulfur iodine process remains a very promising solution in matter of efficiency and cost. This work provides a pre-conceptual design description of a SI-Based H2-Nuclear Reactor plant. Software based on chemical process simulation (CPS) was used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. (Author)

Thermodynamic consideration on the constitution of multi-thermochemical water splitting process

International Nuclear Information System (INIS)

Tagawa, Hiroaki

1976-03-01

The multi-thermochemical water splitting cycle comprises individual chemical reactions which are generalized as hydrolysis, hydrogen generation, oxygen generation and regeneration of the circulating materials. The circulating agents are required for the constitution of the cycle, but the guiding principle of selecting them is not available yet. In the present report, thermodynamic properties, especially Gibbs free energies for formation, of the agents are examined as a function of temperature. Oxides, sulfo-oxides, chlorides, bromides and iodides are chosen as the compounds. The chemical reactions for hydrolysis, hydrogen generation and oxygen generation are reviewed in detail. The general formulas for the three step splitting cycle are represented with discussion. (auth.)

Synfuels from fusion: producing hydrogen with the tandem mirror reactor and thermochemical cycles

International Nuclear Information System (INIS)

Ribe, F.L.; Werner, R.W.

1981-01-01

This report examines, for technical merit, the combination of a fusion reactor driver and a thermochemical plant as a means for producing synthetic fuel in the basic form of hydrogen. We studied: (1) one reactor type - the Tandem Mirror Reactor - wishing to use to advantage its simple central cell geometry and its direct electrical output; (2) two reactor blanket module types - a liquid metal cauldron design and a flowing Li 2 O solid microsphere pellet design so as to compare the technology, the thermal-hydraulics, neutronics and tritium control in a high-temperature operating mode (approx. 1200 K); (3) three thermochemical cycles - processes in which water is used as a feedstock along with a high-temperature heat source to produce H 2 and O 2

Degradation of materials under conditions of thermochemical cycles for hydrogen production - part III

International Nuclear Information System (INIS)

Klimas, S.J.; Searle, H.; Guerout, F.

2011-01-01

A capsule method was employed to screen a number of materials for degradation under selected conditions of the sulphur-iodine (SI) and the copper-chlorine (Cu-Cl) thermochemical cycles. A summary of the results of an experimental investigation is given. The recommendations for the selection of the materials required for the construction of the electrolyser subsystem of the copper chlorine hybrid cycle are presented and discussed with the associated rationale. Some remaining uncertainties are illustrated on the basis of the experimental evidence gathered. (author)

Advances in hydrogen production by thermochemical water decomposition: A review

International Nuclear Information System (INIS)

Rosen, Marc A.

2010-01-01

Hydrogen demand as an energy currency is anticipated to rise significantly in the future, with the emergence of a hydrogen economy. Hydrogen production is a key component of a hydrogen economy. Several production processes are commercially available, while others are under development including thermochemical water decomposition, which has numerous advantages over other hydrogen production processes. Recent advances in hydrogen production by thermochemical water decomposition are reviewed here. Hydrogen production from non-fossil energy sources such as nuclear and solar is emphasized, as are efforts to lower the temperatures required in thermochemical cycles so as to expand the range of potential heat supplies. Limiting efficiencies are explained and the need to apply exergy analysis is illustrated. The copper-chlorine thermochemical cycle is considered as a case study. It is concluded that developments of improved processes for hydrogen production via thermochemical water decomposition are likely to continue, thermochemical hydrogen production using such non-fossil energy will likely become commercial, and improved efficiencies are expected to be obtained with advanced methodologies like exergy analysis. Although numerous advances have been made on sulphur-iodine cycles, the copper-chlorine cycle has significant potential due to its requirement for process heat at lower temperatures than most other thermochemical processes.

Renewable hydrogen production via thermochemical/electrochemical coupling

Energy Technology Data Exchange (ETDEWEB)

Ambrosini, Andrea [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Babiniec, Sean Michael [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Miller, James E. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

2017-10-01

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 is 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.

Thermoeconomic analysis of a copper-chlorine thermochemical cycle for nuclear-based hydrogen production

International Nuclear Information System (INIS)

Orhan, Mehmet F.; Dincer, Ibrahim; Rosen, Marc A.

2010-01-01

Thermochemical water splitting with a copper-chlorine (Cu-Cl) cycle is a promising process that could be linked with nuclear reactors to decompose water into its constituents, oxygen and hydrogen, through intermediate copper and chlorine compounds. In this paper, a comprehensive exergoeconomic analysis of the Cu-Cl cycle is reported to evaluate the production costs as a function of the amount and quality of the energy used for hydrogen production, as well as the costs of the exergy losses and the exergoeconomic improvement potential of the equipment used in the process. An additional objective is to determine changes in the design parameters of the Cu-Cl cycle that improve the cost effectiveness of the overall system. (orig.)

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

Science.gov (United States)

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.

Ceramic carbon electrode-based anodes for use in the copper-chlorine thermochemical cycle

International Nuclear Information System (INIS)

Ranganathan, S.; Easton, E.B.

2009-01-01

Sol-gel chemistry is becoming more popular for the synthesis of electrode materials. For example, the sol-gel reaction can be performed in the presence of a carbon black to form a ceramic carbon electrode (CCE). The resultant CCE structure contains electronically conductive carbon particle pathways that are bound together via the ceramic binder, which can also promote ion transport. Furthermore, the CCE structure has a high active surface area and is chemical and thermally robust. We have investigated CCE materials prepared using 3-aminopropyl trimethoxysilane. Electrochemical experiments (cyclic voltammetry, electrochemical impedance spectroscopy) were performed to characterize their suitability as anode electrode materials for use in the electrochemical step of the Cu-Cl thermochemical cycle. Our initial results have shown that CCE-based electrodes vastly outperform a bare carbon electrode, and thus are highly promising and cost-effective electrode material. Subsequent experiments involved the manipulation of the relative ratio of organosilane carbon precursors to gauge its impact on electrode properties and performance. An overview of the materials characterization and electrochemical measurements will be presented. (author)

Ceramic carbon electrode-based anodes for use in the copper-chlorine thermochemical cycle

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, S.; Easton, E.B. [Faculty of Science, Univ. of Ontario Inst. of Technology, Oshawa, Ontario (Canada)], E-mail: ranga@uoit.ca, Brad.Easton@uoit.ca

2009-07-01

Sol-gel chemistry is becoming more popular for the synthesis of electrode materials. For example, the sol-gel reaction can be performed in the presence of a carbon black to form a ceramic carbon electrode (CCE). The resultant CCE structure contains electronically conductive carbon particle pathways that are bound together via the ceramic binder, which can also promote ion transport. Furthermore, the CCE structure has a high active surface area and is chemical and thermally robust. We have investigated CCE materials prepared using 3-aminopropyl trimethoxysilane. Electrochemical experiments (cyclic voltammetry, electrochemical impedance spectroscopy) were performed to characterize their suitability as anode electrode materials for use in the electrochemical step of the Cu-Cl thermochemical cycle. Our initial results have shown that CCE-based electrodes vastly outperform a bare carbon electrode, and thus are highly promising and cost-effective electrode material. Subsequent experiments involved the manipulation of the relative ratio of organosilane carbon precursors to gauge its impact on electrode properties and performance. An overview of the materials characterization and electrochemical measurements will be presented. (author)

Analysis of sulfur-iodine thermochemical cycle for solar hydrogen production. Part 1: decomposition of sulfuric acid

Energy Technology Data Exchange (ETDEWEB)

Huang, Cunping; T-Raissi, Ali [Central Florida Univ., Florida Solar Energy Center, Cocoa, FL (United States)

2005-05-01

The sulfur-iodine (S-I) thermochemical water splitting cycle is one of the most studied cycles for hydrogen (H{sub 2}) production. S-I cycle consists of four sections: (I) acid production and separation and oxygen purification, (II) sulfuric acid concentration and decomposition, (III) hydroiodic acid (HI) concentration, and (IV) HI decomposition and H{sub 2} purification. Section II of the cycle is an endothermic reaction driven by the heat input from a high temperature source. Analysis of the S-I cycle in the past thirty years have been focused mostly on the utilization of nuclear power as the high temperature heat source for the sulfuric acid decomposition step. Thermodynamic as well as kinetic considerations indicate that both the extent and rate of sulfuric acid decomposition can be improved at very high temperatures (in excess of 1000 deg C) available only from solar concentrators. The beneficial effect of high temperature solar heat for decomposition of sulfuric acid in the S-I cycle is described in this paper. We used Aspen Technologies' HYSYS chemical process simulator (CPS) to develop flowsheets for sulfuric acid (H{sub 2}SO{sub 4}) decomposition that include all mass and heat balances. Based on the HYSYS analyses, two new process flowsheets were developed. These new sulfuric acid decomposition processes are simpler and more stable than previous processes and yield higher conversion efficiencies for the sulfuric acid decomposition and sulfur dioxide and oxygen formation. (Author)

Assessment of thermochemical hydrogen production. Project 8994 mid-contract progress report, July 1--November 1, 1977. [Iron chloride and copper sulfate cycles

Energy Technology Data Exchange (ETDEWEB)

Dafler, J.R.; Foh, S.E.; Schreiber, J.D.

1977-12-01

We have completed the base-case (first-cut) flowsheet analysis for two thermochemical water-splitting cycles that have been under study at the Institute of Gas Technology: a four-step iron chloride cycle (denoted B-1) and a four-step copper sulfate cycle (denoted H-5). In the case of Cycle B-1, an energy balance has located the worst problem areas in the cycle, and flowsheet modifications have begun. Calculations of equilibrium effects due to the hydrolysis of ferrous chloride at pressures high enough to interface with projected hydrogen transmission systems will, apparently, necessitate higher temperature process heat input for this step. Higher pressure operation of some critical separation processes yields more favorable heat balances. For Cycle H-5, the unmodified (base-case) flowsheet indicates that reaction product separations will be relatively simple with respect to Cycle B-1. Work of Schuetz and others dealing with the electrolysis and thermodynamics of HBr/H/sub 2/O/SO/sub 2/ systems is being extensively reviewed. Work plans for this part of the contract are currently being reviewed.

CFD Studies on Biomass Thermochemical Conversion

Directory of Open Access Journals (Sweden)

Lifeng Yan

2008-06-01

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

Ceramic carbon electrode-based anodes for use in the Cu-Cl thermochemical cycle

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, Santhanam; Easton, E. Bradley [Faculty of Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario (Canada)

2010-05-15

We have investigated CCE materials prepared using 3-aminopropyl trimethoxysilane. Electrochemical experiments were performed to characterize their suitability as anode electrode materials for use in the electrochemical step of the Cu-Cl thermochemical cycle. CCE-based electrodes vastly outperform a bare carbon electrode. Optimization of the organosilicate loading revealed maximum electrode performance was achieved with 36 wt% and was explained in terms of the optimal balance of active area and anion transport properties. (author)

An overview of R and D activities for the Cu-Cl, cycle with emphasis on the hydrolysis reaction

International Nuclear Information System (INIS)

Lewis, M.A.; Ferrandon, M.S.; Tatterson, D.F.

2010-01-01

This paper describes the status of the development effort for the Cu-Cl thermochemical cycle. Most of the recent work has been focused on the hydrolysis reaction, which is challenging because of the need for excess steam to achieve high yields. Two types of spray reactors were tested and the ultrasonic nozzle gave excellent results. The conceptual process design for the overall process now includes a spray reactor. Engineering methods to increase efficiency are proposed. Preliminary values for the efficiency and capital costs for producing hydrogen using the Cu-Cl cycle have been calculated. (authors)

Development of a seasonal thermochemical storage system

NARCIS (Netherlands)

Cuypers, R.; Maraz, N.; Eversdijk, J.; Finck, C.J.; Henquet, E.M.P.; Oversloot, H.P.; Spijker, J.C. van 't; Geus, A.C. de

2012-01-01

In our laboratories, a seasonal thermochemical storage system for dwellings and offices is being designed and developed. Based on a thermochemical sorption reaction, space heating, cooling and generation of domestic hot water will be achieved with up to 100% renewable energy, by using solar energy

Coupling of copper-chloride hybrid thermochemical water splitting cycle with a desalination plant for hydrogen production from nuclear energy

International Nuclear Information System (INIS)

Orhan, Mehmet F.; Dincer, Ibrahim; Naterer, Greg F.; Rosen, Marc A.

2010-01-01

Energy and environmental concerns have motivated research on clean energy resources. Nuclear energy has the potential to provide a significant share of energy supply without contributing to environmental emissions and climate change. Nuclear energy has been used mainly for electric power generation, but hydrogen production via thermochemical water decomposition provides another pathway for the utilization of nuclear thermal energy. One option for nuclear-based hydrogen production via thermochemical water decomposition uses a copper-chloride (Cu-Cl) cycle. Another societal concern relates to supplies of fresh water. Thus, to avoid causing one problem while solving another, hydrogen could be produced from seawater rather than limited fresh water sources. In this study we analyze a coupling of the Cu-Cl cycle with a desalination plant for hydrogen production from nuclear energy and seawater. Desalination technologies are reviewed comprehensively to determine the most appropriate option for the Cu-Cl cycle and a thermodynamic analysis and several parametric studies of this coupled system are presented for various configurations. (author)

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

Science.gov (United States)

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

Thermochemical reactivity of 5–15 mol% Fe, Co, Ni, Mn-doped cerium oxides in two-step water-splitting cycle for solar hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Gokon, Nobuyuki, E-mail: ngokon@eng.niigata-u.ac.jp [Center for Transdisciplinary Research, Niigata University, 8050 Ikarashi 2-nocho, Nishi-ku, Niigata 950-2181 (Japan); Suda, Toshinori [Graduate School of Science and Technology, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181 (Japan); Kodama, Tatsuya [Department of Chemistry & Chemical Engineering, Faculty of Engineering, Niigata University, 8050 Ikarashi 2-nocho, Niigata 950-2181 (Japan)

2015-10-10

Highlights: • 5–15 mol% M-doped ceria are examined for thermochemical two-step water-splitting. • 5 mol% Fe- and Co-doped ceria have stoichiometric production of oxygen and hydrogen. • 10–15 mol% Fe- and Mn-doped ceria showed near-stoichiometric production. - Abstract: The thermochemical two-step water-splitting cycle using transition element-doped cerium oxide (M–CeO{sub 2−δ}; M = Fe, Co, Ni, Mn) powders was studied for hydrogen production from water. The oxygen/hydrogen productivity and repeatability of M–CeO{sub 2−δ} materials with M doping contents in the 5–15 mol% range were examined using a thermal reduction (TR) temperature of 1500 °C and water decomposition (WD) temperatures in the 800–1150 °C range. The temperature, steam partial pressure, and steam flow rate in the WD step had an impact on the hydrogen productivity and production rate. 5 mol% Fe- and Co-doped CeO{sub 2−δ} enhances hydrogen productivity by up to 25% on average compared to undoped CeO{sub 2}, and shows stable repeatability of stoichiometric oxygen and hydrogen production for the cyclic thermochemical two-step water-splitting reaction. In addition, 5 mol% Mn-doped CeO{sub 2−δ}, 10 and 15 mol% Fe- and Mn-doped CeO{sub 2−δ} show near stoichiometric reactivities.

Mitigation of climate change via a copper-chlorine hybrid thermochemical water splitting cycle for hydrogen production from nuclear energy

International Nuclear Information System (INIS)

Orhan, M.F.; Dincer, I.; Rosen, M.A.

2009-01-01

Concerns regarding climate change have motivated research on clean energy resources. While many energy resources have limitations, nuclear energy has the potential to supply a significant share of energy supply without contributing to climate change. Nuclear energy has been used mainly for electric power generation, but hydrogen production via thermochemical water decomposition provides another option for the utilization of nuclear thermal energy. This paper describes nuclear-based hydrogen production technologies and discusses the role of the Cu-Cl cycle for thermochemical water decomposition, potentially driven in part by waste heat from a nuclear generating station, in reducing greenhouse gas emissions. (author)

Degradation of materials under conditions of thermochemical cycles for hydrogen production

International Nuclear Information System (INIS)

Klimas, S.J.; Searle, H.; Stolberg, L.

2010-01-01

A capsule method has been developed and employed to measure the degradation rates of selected materials under some of the most challenging conditions relevant to the sulphur-iodine (SI) and the copper-chlorine (Cu-Cl) thermochemical cycles for hydrogen production. The materials tested so far include metals and engineering alloys, structural and functional polymers, elastomers, carbon-based materials, ceramics and glasses, and composites. A number of characterization methods have been used to detect and quantify the degradation of the diverse materials and, when feasible, establish the mode of attack. The paper details the results of this ongoing experimental investigation. The investigation currently focuses on the copper-chlorine hybrid cycle. The environment representative of the conditions in the electrolyser subsystem was approximated with an aqueous solution of hydrochloric acid (13.6 mol/kg), copper(II) chloride (1.36 mol/kg) and copper(I) chloride (1.36 mol/kg) at 160°C and 2.5 MPa (absolute). The current (tentative) recommendations for the selection of the materials required for the construction of the electrolyser subsystem of the copper-chlorine hybrid cycle, and the associated rationale, are presented and discussed. (author)

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

Werner, R.W.

1982-01-01

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 2 SO 4 -H 2 O system

Analysis of the hybrid copper oxide-copper sulfate cycle for the thermochemical splitting of water for hydrogen production

International Nuclear Information System (INIS)

Gonzales, Ross B.; Law, Victor J.; Prindle, John C.

2009-01-01

The hybrid copper oxide-copper sulfate water-splitting thermochemical cycle involves two principal steps: (1) hydrogen production from the electrolysis of water, SO 2 (g) and CuO(s) at room temperature and (2) the thermal decomposition of the CuSO 4 product to form oxygen and SO 2 , which is recycled to the first step. A four-reaction version of the cycle (known in the literature as Cycle H-5) was used as the basis of the present work. For several of the four reactions, a rotating batch reactor sequence is proposed in order to overcome equilibrium limitations. Pinch technology was used to optimize heat integration. Sensitivity analyses revealed it to be economically more attractive to use a 10 C approach to minimize heat loss (rather than 20 C). Using standard Aspen Plus features and the Peng-Robinson equation of state for separations involving oxygen and sulfur oxides, a proposed flowsheet for the cycle was generated to yield ''Level 3'' results. A cost analysis of the designed plant (producing 100 million kmol/yr hydrogen) indicates a total major equipment cost of approximately $45 million. This translates to a turnkey plant price (excluding the cost of the high-temperature heat source or electrolyzer internals) of approximately $360 million. Based on a $2.50/kg selling price for hydrogen, gross annual revenue could be on the order of $500 million, resulting in a reasonable payback period when all capital and operating costs are considered. Previous efficiency estimates using Level 1 and Level 2 methods gave the process efficiency in the neighborhood of 47-48%. The Level 3 efficiency computation was 24-25% depending on the approach temperature used for recuperation. If the low quality heat rejected by the process can be recovered and used elsewhere, the Level 3 analysis could be as high as 51-53%. (author)

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

Energy Technology Data Exchange (ETDEWEB)

Werner, R.W. (ed.)

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 performance analysis of solar driven CO_2 methane reforming

International Nuclear Information System (INIS)

Fuqiang, Wang; Jianyu, Tan; Huijian, Jin; Yu, Leng

2015-01-01

Increasing CO_2 emission problems create urgent challenges for alleviating global warming, and the capture of CO_2 has become an essential field of scientific research. In this study, a finite volume method (FVM) coupled with thermochemical kinetics was developed to analyze the solar driven CO_2 methane reforming process in a metallic foam reactor. The local thermal non-equilibrium (LTNE) model coupled with radiative heat transfer was developed to provide more temperature information. A joint inversion method based on chemical process software and the FVM coupled with thermochemical kinetics was developed to obtain the thermochemical reaction parameters and guarantee the calculation accuracy. The detailed thermal and thermochemical performance in the metal foam reactor was analyzed. In addition, the effects of heat flux distribution and porosity on the solar driven CO_2 methane reforming process were analyzed. The numerical results can serve as theoretical guidance for the solar driven CO_2 methane reforming application. - Highlights: • Solar driven CO_2 methane reforming process in metal foam reactor is analyzed. • FVM with chemical reactions was developed to analyze solar CO_2 methane reforming. • A joint inversion method was developed to obtain thermochemical reaction parameters. • Results can be a guidance for the solar driven CO_2 methane reforming application.

Maximizing Efficiency in Two-step Solar-thermochemical Fuel Production

Energy Technology Data Exchange (ETDEWEB)

Ermanoski, I. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

2015-05-01

Widespread solar fuel production depends on its economic viability, largely driven by the solar-to-fuel conversion efficiency. In this paper, the material and energy requirements in two-step solar-thermochemical cycles are considered.The need for advanced redox active materials is demonstrated, by considering the oxide mass flow requirements at a large scale. Two approaches are also identified for maximizing the efficiency: optimizing reaction temperatures, and minimizing the pressure in the thermal reduction step by staged thermal reduction. The results show that each approach individually, and especially the two in conjunction, result in significant efficiency gains.

Thermochemical production of hydrogen from water

International Nuclear Information System (INIS)

Funk, J.E.; Conger, W.L.; Carty, R.H.; Barker, R.E.

1975-01-01

A review of recent developments in the selection and evaluation of multi-step thermochemical water-splitting cycles is presented. A computerized and thermodynamic and chemical engineering analysis procedure is discussed with calculates, among other things, the thermal efficiency of the process which is defined to be the ratio of the enthalpy change for water decomposition to the total thermal energy required by the process. Changes in the thermodynamic state in each step of the process are also determined. Engineering considerations such as the effect of approach to equilibrium in the chemical reaction steps on the work of separation, and the magnitude of the recycle streams are included. Important practical matters such as thermal regeneration in the product and reactant streams are dealt with in some detail. The effect of reaction temperature on thermal efficiency is described and the use of the analysis procedure is demonstrated by applying it to several processes. (author)

New applications with time-dependent thermochemical simulation

Energy Technology Data Exchange (ETDEWEB)

Koukkari, P. [VTT Chemical Technology, Espoo (Finland); Laukkanen, L. [VTT Automation, Espoo (Finland); Penttilae, K. [Kemira Engineering Oy, Helsinki (Finland)

1996-12-31

A new method (RATEMIX) to calculate multicomponent chemical reaction mixtures as a series of sequential thermochemical states was recently introduced. The procedure combines multicomponent thermodynamics with chemical kinetics and may be used to simulate the multicomponent reactors as a thermochemical natural process. The method combines the desired reaction rates sequentially with constrained Gibbs energy minimization. The reactant concentrations are determined by the experimental (Arrhenius) rate laws. During the course of the given reaction the subsequent side reactions are supposed to occur reversibly. At every sequential stage of the given reaction the temperature and composition of the reaction mixture are calculated by a thermodynamic subroutine, which minimizes the Gibbs energy of the system and takes into account the heat transfer between the system and its surroundings. The extents of reaction are included as algorithmic constraints in the Gibbs energy minimization procedure. Initially, the reactants are introduced to the system as inert copies to match both the mass and energy balance of the reactive system. During the calculation the copies are sequentially interchanged to the actual reactants which allows one to simulate the time-dependent reaction route by using the thermochemical procedure. For each intermediate stage, the temperature and composition are calculated and as well numerical estimates of the thermodynamic functions are obtained. The method is applicable in processes where the core thermodynamic and kinetic data of the system are known and the time-dependent heat transfer data can either be measured or estimated by calculation. The method has been used to simulate e.g. high temperature flame reactions, zinc vapour oxidation and a counter-current rotary drum with chemical reactions. The procedure has today been tested with SOLGASMIX, CHEMSAGE and HSC programs. (author)

New applications with time-dependent thermochemical simulation

Energy Technology Data Exchange (ETDEWEB)

Koukkari, P [VTT Chemical Technology, Espoo (Finland); Laukkanen, L [VTT Automation, Espoo (Finland); Penttilae, K [Kemira Engineering Oy, Helsinki (Finland)

1997-12-31

A new method (RATEMIX) to calculate multicomponent chemical reaction mixtures as a series of sequential thermochemical states was recently introduced. The procedure combines multicomponent thermodynamics with chemical kinetics and may be used to simulate the multicomponent reactors as a thermochemical natural process. The method combines the desired reaction rates sequentially with constrained Gibbs energy minimization. The reactant concentrations are determined by the experimental (Arrhenius) rate laws. During the course of the given reaction the subsequent side reactions are supposed to occur reversibly. At every sequential stage of the given reaction the temperature and composition of the reaction mixture are calculated by a thermodynamic subroutine, which minimizes the Gibbs energy of the system and takes into account the heat transfer between the system and its surroundings. The extents of reaction are included as algorithmic constraints in the Gibbs energy minimization procedure. Initially, the reactants are introduced to the system as inert copies to match both the mass and energy balance of the reactive system. During the calculation the copies are sequentially interchanged to the actual reactants which allows one to simulate the time-dependent reaction route by using the thermochemical procedure. For each intermediate stage, the temperature and composition are calculated and as well numerical estimates of the thermodynamic functions are obtained. The method is applicable in processes where the core thermodynamic and kinetic data of the system are known and the time-dependent heat transfer data can either be measured or estimated by calculation. The method has been used to simulate e.g. high temperature flame reactions, zinc vapour oxidation and a counter-current rotary drum with chemical reactions. The procedure has today been tested with SOLGASMIX, CHEMSAGE and HSC programs. (author)

Decomposition analysis of cupric chloride hydrolysis in the Cu-Cl cycle of hydrogen production

International Nuclear Information System (INIS)

Daggupati, V.N.; Naterer, G.F.; Gabriel, K.S.; Gravelsins, R.; Wang, Z.

2009-01-01

This paper examines cupric chloride solid conversion during hydrolysis in a thermochemical copper-chlorine (Cu-Cl) cycle for hydrogen production. The hydrolysis reaction is a challenging step, in terms of the excess steam requirement and the decomposition of cupric chloride (CuCl 2 ) into cuprous chloride (CuCl) and chlorine (Cl 2 ). The hydrolysis and decomposition reactions are analyzed with respect to the chemical equilibrium constant. The effects of operating parameters are examined, including the temperature, pressure, excess steam and equilibrium conversion. A maximization of yield and selectivity are very important. Rate constants for the simultaneous reaction steps are determined using a uniform reaction model. A shrinking core model is used to determine the rate coefficients and predict the solid conversion time, with diffusional and reaction control. These new results are useful for scale-up of the engineering equipment in the thermochemical Cu-Cl cycle for hydrogen production. (author)

Capabilities to Support Thermochemical Hydrogen Production Technology Development

Energy Technology Data Exchange (ETDEWEB)

Daniel M. Ginosar

2009-05-01

This report presents the results of a study to determine if Idaho National Laboratory (INL) has the skilled staff, instrumentation, specialized equipment, and facilities required to take on work in thermochemical research, development, and demonstration currently being performed by the Nuclear Hydrogen Initiative (NHI). This study outlines the beneficial collaborations between INL and other national laboratories, universities, and industries to strengthen INL's thermochemical efforts, which should be developed to achieve the goals of the NHI in the most expeditious, cost effective manner. Taking on this work supports INL's long-term strategy to maintain leadership in thermochemical cycle development. This report suggests a logical path forward to accomplish this transition.

Thermodynamic of the associated cycle and application to the assembly of thermochemical iodine sulphur cycle and a nuclear engine for the hydrogen production

International Nuclear Information System (INIS)

Dumont, Y.

2008-01-01

This thesis is devoted to the design of an assembly of a hydrogen production process by the thermochemical iodine-sulphur cycle and a nuclear reactor. The suggested coupling network uses a power cycle which produces a work which is directly used for the heat pump running. The purpose of this thermodynamic cycle association is to recover the rejected energy at low temperature of a process to provide the energy needs of this same process at high temperature. This association is applied to the studied coupling. The construction of the energy distribution network is designed by the pinch analysis. In the case of a conventional coupling, the efficiency of hydrogen production is 22.0%. By integrating the associated cycles into the coupling, the efficiency of production is 42.6%. The exergetic efficiency, representative of the energy using quality, increases from 58.7% to 85.4%. (author) [fr

Effects of key factors on solar aided methane steam reforming in porous medium thermochemical reactor

International Nuclear Information System (INIS)

Wang, Fuqiang; Tan, Jianyu; Ma, Lanxin; Leng, Yu

2015-01-01

Highlights: • Effects of key factors on chemical reaction for solar methane reforming are studied. • MCRT and FVM method coupled with UDFs is used to establish numerical model. • Heat and mass transfer model coupled with thermochemical reaction is established. • LTNE model coupled with P1 approximation is used for porous matrix solar reactor. • A formula between H 2 production and conductivity of porous matrix is put forward. - Abstract: With the aid of solar energy, methane reforming process can save up to 20% of the total methane consumption. Monte Carlo Ray Tracing (MCRT) method and Finite Volume Method (FVM) combined method are developed to establish the heat and mass transfer model coupled with thermochemical reaction kinetics for porous medium solar thermochemical reactor. In order to provide more temperature information, local thermal non-equilibrium (LTNE) model coupled with P1 approximation is established to investigate the thermal performance of porous medium solar thermochemical reaction. Effects of radiative heat loss and thermal conductivity of porous matrix on temperature distribution and thermochemical reaction for solar driven steam methane reforming process are numerically studied. Besides, the relationship between hydrogen production and thermal conductivity of porous matrix are analyzed. The results illustrate that hydrogen production shows a 3 order polynomial relation with thermal conductivity of porous matrix

Studies on closed-cycle processes for hydrogen production, 3

International Nuclear Information System (INIS)

Sato, Shoichi; Ikezoe, Yasumasa; Shimizu, Saburo; Nakajima, Hayato; Kobayashi, Toshiaki

1978-10-01

Studies made in fiscal 1977 on the thermochemical and radiation chemical processes for hydrogen production are reported. In the thermochemical process, cerium (III) carbonate was used as an intermediate, and a workable process was found, which consisted of eight reaction steps. In other feasible processes, carbon dioxide was made to react with iron (II) chloride or iodide at high temperature to form carbon monoxide, and three or four reaction steps ensued. Also, an improved process of the sulfur cycle was studied. In this process, nickel salts were separated by solvent extraction. Estimated thermal efficiency (HHV) of the process was 30 - 40%, assuming 70 - 80% heat recovery. In the radiation chemical process, carbon dioxide was added with propane or nitrogen dioxide and radiolyzed: reaction mechanisms are discussed. (author)

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

Science.gov (United States)

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

Effect of liquid sodium thermochemical reactions with stainless steels on mechanical response

International Nuclear Information System (INIS)

Subbaraman, G.; Reifsnider, K.L.

1976-01-01

An analytical approach is presented to study the elastic response of an LMFBR fuel clad subject to strong property degradation in liquid sodium environment and internal poison pressure, at the gas plenum section of the fuel pin. The nature and analysis of the thermochemical reactions and the available experimental data are briefly reviewed. Property variations in the radial direction due to these inservice reactions are represented by a generalized, continuous function, f(r), which is introduced into the constitutive equations of stress equilibrium. By introducing an adjustable constant A into a specific form of f(r), various severities in the variation of the elastic parameters through the thickness of the clad are accommodated and particular analytical solutions are obtained for the displacement. Closed form solutions, which are available for particular values of A, are used as validity checks in computing the more general solutions. The stress-strain responses including the deviatoric stresses used in creep analyses are presented for several cases. The merits of the analytical formulation of the problem and the need to include similar approaches in fuel performance calculations are stated

Catalytic performance and durability of Ni/AC for HI decomposition in sulfur–iodine thermochemical cycle for hydrogen production

International Nuclear Information System (INIS)

Fu, Guangshi; He, Yong; Zhang, Yanwei; Zhu, Yanqun; Wang, Zhihua; Cen, Kefa

2016-01-01

Highlights: • The relation between Ni content and Ni particle dispersion were disclosed. • The effect of Ni content on the catalytic activity of Ni/AC catalyst was revealed. • The optimal content of Ni for Ni/AC catalysts in HI decomposition was found. - Abstract: This work reports the Ni content effect on the Ni/AC catalytic performance in the HI decomposition reaction of the sulfur–iodine (SI) thermochemical cycle for hydrogen production and the Ni/AC catalyst durability in a long-term test. Accordingly, five catalysts with the Ni content ranging from 5% to 15% were prepared by an incipient-wetness impregnation method. The activity of all catalysts was examined under the temperature range of 573–773 K. The catalytic performance evaluation suggests that Ni content plays a significant role in the Ni dispersion, Ni particle size, and eventually the catalytic activity in HI decomposition. 12% is the optimal Ni content for Ni/AC catalysts in HI decomposition which is balanced between poor dispersion of Ni particles and increasing active center. The results of 24 h durability test, which incorporated with BET and TEM investigations of the 12%Ni/AC catalyst before and after the reaction, indicate that establishing a better Ni particle dispersion pattern and improving the stability of Ni particles on the support should be considered in the future.

Entropy Analysis of Solar Two-Step Thermochemical Cycles for Water and Carbon Dioxide Splitting

Directory of Open Access Journals (Sweden)

Matthias Lange

2016-01-01

Full Text Available The present study provides a thermodynamic analysis of solar thermochemical cycles for splitting of H2O or CO2. Such cycles, powered by concentrated solar energy, have the potential to produce fuels in a sustainable way. We extend a previous study on the thermodynamics of water splitting by also taking into account CO2 splitting and the influence of the solar absorption efficiency. Based on this purely thermodynamic approach, efficiency trends are discussed. The comprehensive and vivid representation in T-S diagrams provides researchers in this field with the required theoretical background to improve process development. Furthermore, results about the required entropy change in the used redox materials can be used as a guideline for material developers. The results show that CO2 splitting is advantageous at higher temperature levels, while water splitting is more feasible at lower temperature levels, as it benefits from a great entropy change during the splitting step.

Hydrogen production by the iodine-sulphur thermochemical cycle. Total and partial pressure measurements

International Nuclear Information System (INIS)

D Doizi; V Dauvois; J L Roujou; V Delanne; P Fauvet; B Larousse; O Hercher; P Carles; C Moulin

2006-01-01

The iodine sulphur thermochemical cycle appears to be one of the most promising candidate for the massive production of hydrogen using nuclear energy. The key step in this cycle is the HI distillation section which must be optimized to get a good efficiency of the overall cycle. The concept of reactive versus extractive distillation of HI has been proposed because of its potentiality. The design and the optimization of the reactive distillation column requires the knowledge of the liquid vapour equilibrium over the ternary HI-I 2 -H 2 O mixtures up to 300 C and 100 bars. A general methodology based on three experimental devices imposed by the very corrosive and concentrated media will be described: 1) I1 for the total pressure measurement versus different ternary compositions. 2) I2 for the partial and total pressure measurements around 130 C and 2 bars to validate the choice of the analytical optical 'online' techniques we have proposed. 3) I3 for the partial and total pressures measurements in the process domain. The results obtained on pure samples, binary mixtures HI-H 2 O and ternary mixtures using an experimental design analysis in the experimental device I2 will be discussed. (authors)

Novel separation process of gaseous mixture of SO2 and O2 with ionic liquid for hydrogen production in thermochemical sulfur-iodine water splitting cycle

International Nuclear Information System (INIS)

Kim, Chang Soo; Gong, Gyeong Taek; Yoo, Kye Sang; Kim, Honggon; Lee, Byoung Gwon; Ahn, Byoung Sung; Jung, Kwang Deog; Lee, Ki Yong; Song, Kwang Ho

2007-01-01

Sulfur-Iodine cycle is the most promising thermochemical cycle for water splitting to produce hydrogen which can replace the fossil fuels in the future. As a sub-cycle in the thermochemical Sulfur-Iodine water splitting cycle, sulfuric acid (H 2 SO 4 ) decomposes into oxygen (O 2 ) and sulfur dioxide (SO 2 ) which should be separated for the recycle of SO 2 into the sulfuric acid generation reaction (Bunsen Reaction). In this study, absorption and desorption process of SO 2 by ionic liquid which is useful for the recycle of SO 2 into sulfuric acid generation reaction after sulfuric acid decomposition in the thermochemical Sulfur-Iodine cycle is investigated. At first, the operability as an absorbent for the SO 2 absorption and desorption at high temperature without the volatilization of absorbents which is not suitable for the recycle of absorbent-free SO 2 after the absorption process. The temperature range of operability is determined by TGA and DTA analysis. Most of ionic liquids investigated are applicable at high temperature desorption without volatility around 300 deg. C except [BMIm] Cl, and [BMIm] OAc which show the decomposition of ionic liquids. To evaluate the capability of SO 2 absorption, each ionic liquid is located in the absorption tube and gaseous SO 2 is bubbled into the ionic liquid. During the bubbling, the weight of the system is measured and converted into the absorbed SO 2 amount at each temperature controlled by the heater. Saturated amounts of absorbed SO 2 by ionic liquids at 50 deg. C are presented. The effect of anions for the SO 2 absorption capability is shown in the order of Cl, OAc, MeSO 3 , BF 4 , MeSO 4 , PF 6 , and HSO 4 when they are combined with [BMIm] cation. [BMIm]Cl has the largest amount of SO 2 absorbed which can be the most promising absorbent; however, from the point of operability at high temperature which includes desorption process, [BMIm]Cl is vulnerable to high temperature around 250 deg. C based on the TGA

Assessment of a closed thermochemical energy storage using energy and exergy methods

International Nuclear Information System (INIS)

Abedin, Ali Haji; Rosen, Marc A.

2012-01-01

Highlights: ► Thermodynamics assessments are reported for a general closed thermochemical thermal energy storage system. ► Energy and exergy efficiencies of various processes in a closed thermochemical TES are evaluated and compared. ► Understanding is enhanced of thermochemical TES technologies and their potential implementations. ► Exergy analysis is observed to be useful when applied to thermochemical TES, with or in place of energy analysis. - Abstract: Thermal energy storage (TES) is an important technology for achieving more efficient and environmentally benign energy systems. Thermochemical TES is a type of TES with the potential for high energy density and is only recently being considered intensively. To improve understanding of thermochemical TES systems and their implementation, energy and exergy analyses are beneficial. Here, thermodynamics assessments are presented for a general closed thermochemical TES system, including assessments and comparisons of the efficiencies of the overall thermochemical TES cycle and its charging, storing and discharging processes. Locations and causes of thermodynamic losses in thermochemical TES systems are being specified using exergy analysis. The analytical methodology applied in this study identifies that energy and exergy efficiencies differ for thermochemical TESs, e.g. the energy efficiency for a case study is approximately 50% while the exergy efficiency is about 10%. Although the focus is to evaluate thermodynamic efficiencies, other design parameters such as cost, and environmental impact also need to be examined in assessing thermochemical storage. The efficiencies for thermochemical TES provided here should be helpful for designing these energy systems and enhancing their future prospects.

Thermophysical properties of copper compounds in copper-chlorine thermochemical water splitting cycles

International Nuclear Information System (INIS)

Zamfirescu, C.; Dincer, I.; Naterer, G.F.

2009-01-01

This paper examines the relevant thermophysical properties of compounds of chlorine and copper that are found in thermochemical water splitting cycles. There are four variants of such Cu-Cl cycles that use heat and electricity to split the water molecule and produce H 2 and O 2 . Since the energy input is mainly in the form of thermal energy, the Cu-Cl water splitting cycle is much more efficient than water electrolysis, if the electricity generation efficiency for electrolysis is taken into account. A number of copper compounds (Cu 2 OCl 2 , CuO, CuCl 2 , CuCl) and other chemicals (Cu, HCl) are recycled within the plant, while the overall effect is splitting of the water molecule. The system includes a number of chemical reactors, heat exchangers, spray dryer and electrochemical cell. This paper identifies the available experimental data for properties of copper compounds relevant to the Cu-Cl cycle analysis and design. It also develops new regression formulas to correlate the properties, which include: specific heat, enthalpy, entropy, Gibbs free energy, density, formation enthalpy and free energy. No past literature data is available for the viscosity and thermal conductivity of molten CuCl, so estimates are provided. The properties are evaluated at 1 bar and a range of temperatures from ambient to 675-1000K, which are consistent with the operating conditions of the cycle. Updated calculations of chemical exergies are provided as follows: 21.08, 6.268, 82.474, and 75.0 kJ/mol for Cu 2 OCl 2 , CuO, CuCl 2 and CuCl, respectively. For molten CuCl, the estimated viscosity varies from 2.6 to 1.7mPa.s. (author)

Thermochemical data for reactor materials

International Nuclear Information System (INIS)

Ronchi, C.; Turrini, F.

1990-01-01

This report describes a computer database of thermochemical properties of nuclear reactor materials to be used for source term calculations in reactor accident codes. In the first part, the structure and the content of the computer file is described. In the second part a set of thermochemical data is presented pertaining to chemical reactions occurring during severe nuclear reactor accidents and involving fuel (uranium dioxide), fission products and structural materials. These data are complementary to those collected in the databook recently published by Cordfunke and Potter after a study supported by the Commission of the European Communities. The present data were collected from review articles and databanks and follow a discussion on the uncertainties and errors involved in the calculation of complex chemical equilibria in the extrapolated temperature range

Achievement report for 1st phase (fiscal 1974-80) Sunshine Program research and development - Hydrogen energy. Research on hydrogen production technology using thermochemical process (Research on cycles of Fe systems etc.); 1974-1980 nendo suiso energy seika hokokusho. Netsu kagakuho ni yoru suiso seizo gijutsu no kenkyu (tetsukei cycle nado no kenkyu)

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-03-01

Collected in this report are the results of efforts of the Government Industrial Research Institute, Osaka, in the 7-year period that began in fiscal 1974. The Institute, after looking for basic reactions in thermochemical cycles which are promising, has come to propose a new cycle in which iron and bromine are the reactants. In the research, the Fe-Br reaction is divided into a hydrogen generating loop and an oxygen generating loop, both to be developed into devices. Problems in developing them into a cycle are isolated, and solved. In the hydrogen generating loop, the use of a molten salt is contrived for the prevention of reduction in the reactivity of the Fe{sub 3}O{sub 4} to be generated, and now it is expected that the problem will be solved. No problem is detected in the oxygen generating loop. The process is now accepted as a superb one. As for the materials for the Fe-Br-based cycle apparatus, important tasks have to be undertaken since existing materials cannot be used as is. Besides, thermal efficiency etc. are estimated for a new As-Br-based hybrid cycle and the Fe-Br-based cycle. (NEDO)

Numerical investigation of a straw combustion boiler – Part I: Modelling of the thermo-chemical conversion of straw

Directory of Open Access Journals (Sweden)

Dernbecher Andrea

2016-01-01

Full Text Available In the framework of a European project, a straw combustion boiler in conjunction with an organic Rankine cycle is developed. One objective of the project is the enhancement of the combustion chamber by numerical methods. A comprehensive simulation of the combustion chamber is prepared, which contains the necessary submodels for the thermo-chemical conversion of straw and for the homogeneous gas phase reactions. Part I introduces the modelling approach for the thermal decomposition of the biomass inside the fuel bed, whereas part II deals with the simulation of the gas phase reactions in the freeboard.

The influence of gas–solid reaction kinetics in models of thermochemical heat storage under monotonic and cyclic loading

International Nuclear Information System (INIS)

Nagel, T.; Shao, H.; Roßkopf, C.; Linder, M.; Wörner, A.; Kolditz, O.

2014-01-01

Highlights: • Detailed analysis of cyclic and monotonic loading of thermochemical heat stores. • Fully coupled reactive heat and mass transport. • Reaction kinetics can be simplified in systems limited by heat transport. • Operating lines valid during monotonic and cyclic loading. • Local integral degree of conversion to capture heterogeneous material usage. - Abstract: Thermochemical reactions can be employed in heat storage devices. The choice of suitable reactive material pairs involves a thorough kinetic characterisation by, e.g., extensive thermogravimetric measurements. Before testing a material on a reactor level, simulations with models based on the Theory of Porous Media can be used to establish its suitability. The extent to which the accuracy of the kinetic model influences the results of such simulations is unknown yet fundamental to the validity of simulations based on chemical models of differing complexity. In this article we therefore compared simulation results on the reactor level based on an advanced kinetic characterisation of a calcium oxide/hydroxide system to those obtained by a simplified kinetic model. Since energy storage is often used for short term load buffering, the internal reactor behaviour is analysed under cyclic partial loading and unloading in addition to full monotonic charge/discharge operation. It was found that the predictions by both models were very similar qualitatively and quantitatively in terms of thermal power characteristics, conversion profiles, temperature output, reaction duration and pumping powers. Major differences were, however, observed for the reaction rate profiles themselves. We conclude that for systems not limited by kinetics the simplified model seems sufficient to estimate the reactor behaviour. The degree of material usage within the reactor was further shown to strongly vary under cyclic loading conditions and should be considered when designing systems for certain operating regimes

A general survey of the potential and the main issues associated with the sulfur-iodine thermochemical cycle for hydrogen production using nuclear heat

International Nuclear Information System (INIS)

Vitart, Xavier; Carles, Philippe; Anzieu, Pascal

2008-01-01

The thermochemical sulfur-iodine cycle is studied by CEA with the objective of massive hydrogen production using nuclear heat at high temperature. The challenge is to acquire by the end of 2008 the necessary decision elements, based on a scientific and validated approach, to choose the most promising way to produce hydrogen using a generation IV nuclear reactor. Amongst the thermochemical cycles, the sulfur-iodine process remains a very promising solution in matter of efficiency and cost, versus its main competitor, conventional electrolysis. The sulfur-iodine cycle is a very versatile process, which allows lot of variants for each section which can be adjusted in synergy in order to optimise the whole process. The main part of CEA's program is devoted to the study of the basic processes: new thermodynamics data acquisition, optimisation of water and iodine quantity, optimisation of temperature and pressure in each unit of the flow-sheet and survey of innovative solutions (membrane separations for instance). This program also includes optimisation of a detailed flow-sheet and studies for a hydrogen production plant (design, scale, first evaluations of safety issues and technico-economic questions). This program interacts strongly with other teams, in the framework of international collaborations (Europe, USA for instance). (author)

A general survey of the potential and the main issues associated with the sulfur-iodine thermochemical cycle for hydrogen production using nuclear heat

International Nuclear Information System (INIS)

Vitart, X.; Carles, P.; Anzieu, P.

2008-01-01

The thermochemical sulfur-iodine cycle is studied by CEA with the objective of massive hydrogen production using nuclear heat at high temperature. The challenge is to acquire by the end of 2008 the necessary decision elements, based on a scientific and validated approach, to choose the most promising way to produce hydrogen using a generation IV nuclear reactor. Amongst the thermochemical cycles, the sulfur-iodine process remains a very promising solution in matter of efficiency and cost, versus its main competitor, conventional electrolysis. The sulfur-iodine cycle is a very versatile process, which allows lot of variants for each section which can be adjusted in synergy in order to optimise the whole process. The main part of CEA's program is devoted to the study of the basic processes: new thermodynamics data acquisition, optimisation of water and iodine quantity, optimisation of temperature and pressure in each unit of the flow-sheet and survey of innovative solutions (membrane separations for instance). This program also includes optimisation of a detailed flow-sheet and studies for a hydrogen production plant (design, scale, first evaluations of safety issues and technico-economic questions). This program interacts strongly with other teams, in the framework of international collaborations (Europe, USA for instance). (authors)

Thermochemical Storage of Middle Temperature Wasted Heat by Functionalized C/Mg(OH2 Hybrid Materials

Directory of Open Access Journals (Sweden)

Emanuela Mastronardo

2017-01-01

Full Text Available For the thermochemical performance implementation of Mg(OH2 as a heat storage medium, several hybrid materials have been investigated. For this study, high-performance hybrid materials have been developed by exploiting the authors’ previous findings. Expanded graphite (EG/carbon nanotubes (CNTs-Mg(OH2 hybrid materials have been prepared through Mg(OH2 deposition-precipitation over functionalized, i.e., oxidized, or un-functionalized EG or CNTs. The heat storage performances of the carbon-based hybrid materials have been investigated through a laboratory-scale experimental simulation of the heat storage/release cycles, carried out by a thermogravimetric apparatus. This study offers a critical evaluation of the thermochemical performances of developed materials through their comparison in terms of heat storage and output capacities per mass and volume unit. It was demonstrated that both EG and CNTs improves the thermochemical performances of the storage medium in terms of reaction rate and conversion with respect to pure Mg(OH2. With functionalized EG/CNTs-Mg(OH2, (i the potential heat storage and output capacities per mass unit of Mg(OH2 have been completely exploited; and (ii higher heat storage and output capacities per volume unit were obtained. That means, for technological applications, as smaller volume at equal stored/released heat.

Remarks on the thermochemical production of hydrogen from water using heat from the high temperature reactor

International Nuclear Information System (INIS)

Barnert, H.

1980-06-01

In this report, some aspects of the production of hydrogen from water using heat from the High Temperature Reactor has been studied. These aspects are: the theoretical potential for economic competitivness, the application of hydrogen in the Heat Market, the size of the market potential in the Federal Republic of Germany and the extent of research and development work. In addition another novel proposal for a thermochemical cycle has been studied. For the description of the theoretical potential for economic competitivness, a definition of the 'coupling', has been introduced, which is thermodynamicaly developed; the thermochemical cycle is compared with the thermochemical cycle. Using the coupling, it becomes possible to describe a relation between thermodynamical parameters and the ecomomical basic data of capital costs. Reasons are given from the theoretical point of view for the application of hydrogen as an energy carrier of high exergetic value in the heat market. The discussion of energy problems as 'questions of global survival' leads here to a proposal for the introduction of the term 'extropy'. The market potential in the Federal Republic of Germany is estimated. A further novel proposal for a thermochemical cycle is the 'hydrocarbon-hybrid-process'. The extent of research and development work is explained. (orig.) [de

Natural gas usage as a heat source for integrated SMR and thermochemical hydrogen production technologies

International Nuclear Information System (INIS)

Jaber, O.; Naterer, G.F.; Dincer, I.

2010-01-01

This paper investigates various usages of natural gas (NG) as an energy source for different hydrogen production technologies. A comparison is made between the different methods of hydrogen production, based on the total amount of natural gas needed to produce a specific quantity of hydrogen, carbon dioxide emissions per mole of hydrogen produced, water requirements per mole of hydrogen produced, and a cost sensitivity analysis that takes into account the fuel cost, carbon dioxide capture cost and a carbon tax. The methods examined are the copper-chlorine (Cu-Cl) thermochemical cycle, steam methane reforming (SMR) and a modified sulfur-iodine (S-I) thermochemical cycle. Also, an integrated Cu-Cl/SMR plant is examined to show the unique advantages of modifying existing SMR plants with new hydrogen production technology. The analysis shows that the thermochemical Cu-Cl cycle out-performs the other conventional methods with respect to fuel requirements, carbon dioxide emissions and total cost of production. (author)

Conceptual design study FY 1981: synfuels from fusion - using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

International Nuclear Information System (INIS)

Krikorian, O.H.

1982-01-01

This report represents the second year's effort of a scoping and conceptual design study being conducted for the express purpose of evaluating the engineering potential of producing hydrogen by thermochemical cycles using a tandem mirror fusion driver. The hydrogen thus produced may then be used as a feedstock to produce fuels such as methane, methanol, or gasoline. The main objective of this second year's study has been to obtain some approximate cost figures for hydrogen production through a conceptual design study

Performance analysis of an integrated energy storage and energy upgrade thermochemical solid–gas sorption system for seasonal storage of solar thermal energy

International Nuclear Information System (INIS)

Li, Tingxian; Wang, Ruzhu; Kiplagat, Jeremiah K.; Kang, YongTae

2013-01-01

An innovative dual-mode thermochemical sorption energy storage method is proposed for seasonal storage of solar thermal energy with little heat losses. During the charging phase in summer, solar thermal energy is stored in form of chemical bonds resulting from thermochemical decomposition process, which enables the stored energy to be kept several months at ambient temperature. During the discharging phase in winter, the stored thermal energy is released in the form of chemical reaction heat resulting from thermochemical synthesis process. Thermodynamic analysis showed that the advanced dual-mode thermochemical sorption energy storage is an effective method for the long-term seasonal storage of solar energy. A coefficient of performance (COP h ) of 0.6 and energy density higher than 1000 kJ/kg of salt can be attained from the proposed system. During the discharging phase at low ambient temperatures, the stored thermal energy can be upgraded by use of a solid–gas thermochemical sorption heat transformer cycle. The proposed thermochemical sorption energy storage has distinct advantages over the conventional sensible heat and latent heat storage, such as higher energy storage density, little heat losses, integrated energy storage and energy upgrade, and thus it can contribute to improve the seasonal utilization of solar thermal energy. - Highlights: ► A dual-mode solid thermochemical sorption is proposed for seasonal solar thermal energy storage. ► Energy upgrade techniques into the energy storage system are integrated. ► Performance of the proposed seasonal energy storage system is evaluated. ► Energy density and COP h from the proposed system are as high as 1043 kJ/kg of salt and 0.60, respectively

Towards the renewal of the NEA Thermochemical Database

International Nuclear Information System (INIS)

Ragoussi, Maria-Eleni; Costa, Davide; Bossant, Manuel

2015-01-01

The Thermochemical Database (TDB) Project was created three decades ago as a joint undertaking of the NEA Radioactive Waste Management Committee and the NEA Data Bank. The project involves the collection of high-quality and traceable thermochemical data for a set of elements (mainly minor actinides and fission products) relevant to geophysical modelling of deep geological repositories. Funding comes from 15 participating organisations, primarily national nuclear waste authorities and research institutions. The quantities that are stored in the TDB database are: the standard molar Gibbs energy and enthalpy of formation, the standard molar entropy and, when available, the heat capacity at constant pressure, together with their uncertainty intervals. Reaction data are also provided: equilibrium constant of reaction, molar Gibbs energy of reaction, molar enthalpy of reaction and molar entropy of reaction. Data assessment is carried out by teams of expert reviewers through an in-depth analysis of the available scientific literature, following strict guidelines defined by the NEA to ensure the accuracy and self-consistency of the adopted datasets. Thermochemical data that has been evaluated and selected over the years have been published in the 13 volumes of the Chemical Thermodynamics series. They are also stored in a database that is updated each time the study of a new element is completed. The TDB selected data are made available to external third parties through the NEA web site where data extracted from the database can be displayed and downloaded as plain text files. Following recent recommendations of the Task Force on the Future Programme of the NEA Data Bank to enhance scientific expertise and user services, a renewal of the software managing the TDB database is being undertaken. The software currently used was designed 20 years ago and is becoming obsolete. Redesigning the application will provide an opportunity to correct current shortcomings and to develop

Efficiency of the sulfur-iodine thermochemical water splitting process for hydrogen production based on ADS

International Nuclear Information System (INIS)

Gonzalez, D.; Garcia, L.; Garcia, C.; Garcia, L.; Brayner, C.

2013-01-01

The current hydrogel production is based on fossil fuels; they have a huge contribution to the atmosphere's pollution. thermochemical water splitting cycles don't present this issue because the required process heat is obtained from nuclear energy and therefore, the environmental impact is smaller than using conventional fuels. One of the promising approaches to produce large quantities of hydrogen in an efficient way using nuclear energy is the sulfur-iodine (S-I) thermochemical water splitting cycle. The nuclear source proposed in this paper is a pebble bed gas cooled transmutation facility. Pebble bed very high temperature advanced systems have great perspectives to assume the future nuclear energy. Software based on Chemical Process Simulation (CPS) can be used to simulate the thermochemical water splitting sulfur-iodine cycle for hydrogen production. In this paper, a model for analyzing the sulfur-iodine process sensibility is developed. Efficiency is also calculated and the influence of different parameters on this value. The behavior of the proposed model before different values of initial reactant's flow is analyzed. (Author)

Energy and exergy analyses of a copper-chlorine thermochemical water decomposition pilot plant for hydrogen production

International Nuclear Information System (INIS)

Orhan, M.F.; Dincer, I.; Rosen, M.A.

2008-01-01

Nuclear-based hydrogen production via thermochemical water decomposition using a copper-chlorine (Cu-Cl) cycle consists of a series of chemical reactions in which water is split into hydrogen and oxygen as the net result. This is accomplished through reactions involving intermediate copper and chlorine compounds, which are recycled. Energy and exergy analyses are reported here of a Cu-Cl pilot plant, including the relevant chemical reactions. The reference environment is taken to be at a temperature of 298.15 K and atmospheric pressure (1 atm). The chemical exergy of a substance, which is the maximum work that can be obtained from it by taking it to chemical equilibrium with the reference environment at constant temperature and pressure, is calculated with property data for the substance and the reference environment, with enthalpy and entropy values calculated using Shomate equations. The reaction heat, exergy destruction and efficiencies in each chemical reaction vary with the reaction temperature and reference-environment temperature. A parametric study with variable reaction and reference-environment temperatures is also presented. (author)

High performance ceramic carbon electrode-based anodes for use in the Cu-Cl thermochemical cycle for hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, Santhanam; Easton, E. Bradley [Faculty of Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada)

2010-02-15

A high performance ceramic carbon electrode (CCE) was fabricated by the sol-gel method to study the CuCl electrolysis in Cu-Cl thermochemical cycle. The electrochemical behavior and stability of the CCE was investigated by polarization experiments at different concentrations of CuCl/HCl system. The CCE displayed excellent anodic performance and vastly outperformed the bare carbon fiber paper (CFP) even at high concentrations of CuCl (0.5 M) and HCl (6 M), which is explained in terms of increased active area and enhanced anion transport properties. Further enhancement of activity was achieved by coating the CCE layer onto both sides of the CFP substrate. (author)

Lab-scale experiment of a closed thermochemical heat storage system including honeycomb heat exchanger

International Nuclear Information System (INIS)

Fopah-Lele, Armand; Rohde, Christian; Neumann, Karsten; Tietjen, Theo; Rönnebeck, Thomas; N'Tsoukpoe, Kokouvi Edem; Osterland, Thomas; Opel, Oliver

2016-01-01

A lab-scale thermochemical heat storage reactor was developed in the European project “thermal battery” to obtain information on the characteristics of a closed heat storage system, based on thermochemical reactions. The present type of storage is capable of re-using waste heat from cogeneration system to produce useful heat for space heating. The storage material used was SrBr 2 ·6H 2 O. Due to agglomeration or gel-like problems, a structural element was introduced to enhance vapour and heat transfer. Honeycomb heat exchanger was designed and tested. 13 dehydration-hydration cycles were studied under low-temperature conditions (material temperatures < 100 °C) for storage. Discharging was realized at water vapour pressure of about 42 mbar. Temperature evolution inside the reactor at different times and positions, chemical conversion, thermal power and overall efficiency were analysed for the selected cycles. Experimental system thermal capacity and efficiency of 65 kWh and 0.77 are respectively obtained with about 1 kg of SrBr 2 ·6H 2 O. Heat transfer fluid recovers heat at a short span of about 43 °C with an average of 22 °C during about 4 h, acceptable temperature for the human comfort (20 °C on day and 16 °C at night). System performances were obtained for a salt bed energy density of 213 kWh·m 3 . The overall heat transfer coefficient of the honeycomb heat exchanger has an average value of 147 W m −2  K −1 . Though promising results have been obtained, ameliorations need to be made, in order to make the closed thermochemical heat storage system competitive for space heating. - Highlights: • Lab-scale thermochemical heat storage is designed, constructed and tested. • The use of honeycomb heat exchanger as a heat and vapour process enhancement. • Closed system (1 kg SrBr 2 ·6H 2 O) able to give back 3/4 of initial thermal waste energy. • System storage capacity and thermal efficiency are respectively 65 kWh and 0.77. �

Use of carbon dioxide as a reaction medium in the thermo-chemical process for the enhanced generation of syngas and tuning adsorption ability of biochar

International Nuclear Information System (INIS)

Cho, Dong-Wan; Kwon, Eilhann E.; Song, Hocheol

2016-01-01

Highlights: • Utilizing CO_2 as a reaction medium in thermo-chemical conversion of aquatic biomass. • Enhanced generation of syngas in the presence of CO_2. • Considerable reduction of pyrolytic oil in CO_2-assisted pyrolysis. • Generation of biochar with high surface area and more porous structure by CO_2. - Abstract: This study mechanistically investigated the influences of CO_2 on syngas (H_2 and CO) production during thermo-chemical conversion of red seaweed, and further explored the possible utility of the produced biochar as a medium for adsorption of inorganic/organic contaminants in aqueous phase. In order to elucidate the key roles of CO_2 in the thermo-chemical process, the composition analysis of syngas and the qualitative analysis of pyrolytic oil were conducted and compared with those in pyrolysis in N_2 condition. Pyrolysis of red seaweed in the presence of CO_2 led to the enhanced generation of syngas at the entire experimental temperatures. For example, the ratio of CO to H_2 in the presence of CO_2 at 620 °C was enhanced by ∼400%, as compared to the case in N_2. This enhanced generation of syngas resulted in significant pyrolytic oil reduction by ∼70% at 620 °C via the unknown reactions between VOCs and CO_2. In addition, biochar generated in the CO_2 environment exhibited comparatively higher surface area (61 m"2 g"−"1) and more porous structure. The morphological modification induced by CO_2 provided the favorable condition for removal of methylene blue from the aqueous phase. Thus, this study experimentally demonstrated that exploiting CO_2 as a reaction medium would provide an attractive option for the enhanced generation of syngas and the tuned adsorption capability of biochar.

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

Science.gov (United States)

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 treatment of the pay zone in the well RK-3

Energy Technology Data Exchange (ETDEWEB)

Labudovic, V

1970-02-01

The elements are given for the calculation of the thermochemical treatment of the Well RK-3. From the diagram, the Mg and HCl reaction velocity vs. pressure and the temperature vs. the quantity of the reacted CaCO/sub 3/ can be read out. These are important elements for the calculation of a thermochemical treatment. A comparison of calculated and measured temperatures and the factors influencing the heat conductivity of the formation rock is given. The heating range at formation depths is calculated. The relation quantity of warm acid vs. injection pressure also is given.

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

Science.gov (United States)

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.

Preparation and thermochemical stability of uranium-zirconium-carbonitrides

International Nuclear Information System (INIS)

Kouhsen, C.

1975-08-01

This investigation deals with the preparation and the thermochemical stability of uranium-zirconium-carbonitrides as well as with the mechanism of (U,Zr) (C,N)-preparation by carbothermic reduction of uranium-zirconium-oxide. Single-phase (U,Zr) (C,N)-solid solutions with U:Zr-propertions of 3:1, 1:1, and 1:3 were prepared from oxide powder. The thermochemical stability of the (U,Zr) (C,N)-solid solutions against carbon was measured for varying Zr- and N-contents and for several temperatures; the results indicate an increase of the uranium carbide stability potential by the formation of (U,Zr) (C,N)-solid solutions. The thermodynamic properties ΔG 0 , ΔH 0 , and ΔS 0 were calculated and the correlation between the M(C,N)-lattice constant and the N-content was evaluated. Through an intensive investigation of the reaction mechanism, several different reaction paths were found; for each of them the characteristical diffusion of matter was explained by means of the microsections. It was shown that the Zr-concentration of the oxide reactant and the heating rate during the carbothermic reduction influence the species of the reaction product, especially the homogeneity of the (U,Zr) (C,N)-solid solution. (orig.) [de

Thermodynamic limits on the performance of a solar thermochemical energy storage system

Energy Technology Data Exchange (ETDEWEB)

Lovegrove, K [Australian National Univ., Canberra (Australia). Energy Research Centre

1993-12-01

General expressions for the exergetic and work recovery efficiencies of thermochemical storage systems have been developed by assuming that the reaction process is the only source irreversibility within the closed-loop system. These have been used to plot contours of constant efficiency for the ammonia-based thermochemical system. The effect of spontaneous separation of mixtures due to the preferential condensation of ammonia has been examined analytically and graphically. The analysis presented represents a necessary prerequisite for the optimization of system efficiencies by reactor design. (author)

Deuterium isotope effects in condensed-phase thermochemical decomposition reactions of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine

International Nuclear Information System (INIS)

Shackelford, S.A.; Coolidge, M.B.; Goshgarian, B.B.; Loving, B.A.; Rogers, R.N.; Janney, J.L.; Ebinger, M.H.

1985-01-01

The deuterium isotope effect was applied to condensed-phase thermochemical reactions of HMX and HMX-d 8 by using isothermal techniques. Dissimilar deuterium isotope effects revealed a mechanistic dependence of HMX upon different physical states which may singularly predominate in a specific type of thermal event. Solid-state HMX thermochemical decomposition produces a primary deuterium isotope effect (DIE), indicating that covalent C-H bond rupture is the rate-controlling step in this phase. An apparent inverse DIE is displayed by the mixed melt phase and can be attributed to C-H bond contraction during a weakening of molecular lattice forces as the solid HMX liquefies. The liquid-state decomposition rate appears to be controlled by ring C-N bond cleavage as evidenced by a secondary DIE and higher molecular weight products. These results reveal a dependence of the HMX decomposition process on physical state and lead to a broader mechanistic interpretation which explains the seemingly contradictory data found in current literature reviews. 33 references, 9 figures, 5 tables

Solar Thermochemical Hydrogen Production Research (STCH)

Energy Technology Data Exchange (ETDEWEB)

Perret, Robert [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

2011-05-01

Eight cycles in a coordinated set of projects for Solar Thermochemical Cycles for Hydrogen production (STCH) were self-evaluated for the DOE-EERE Fuel Cell Technologies Program at a Working Group Meeting on October 8 and 9, 2008. This document reports the initial selection process for development investment in STCH projects, the evaluation process meant to reduce the number of projects as a means to focus resources on development of a few most-likely-to-succeed efforts, the obstacles encountered in project inventory reduction and the outcomes of the evaluation process. Summary technical status of the projects under evaluation is reported and recommendations identified to improve future project planning and selection activities.

Assessment of thermochemical hydrogen production. Project 61010 (formerly 8994) final report, July 1, 1977-March 31, 1979

Energy Technology Data Exchange (ETDEWEB)

Dafler, J.R.; Foh, S.E.; Lee, T.S.; Schreiber, J.D.

1979-05-01

The Institute of Gas Technology's (IGT) assessment of thermochemical water-splitting processes is given. Eight tasks were performed: evaluation of load-line efficiencies; hydrogen bromide electrolysis; maximum attainable thermal efficiency on a specific bromide hybrid cycle; development of electrolyzer elements for H/sub 2/SO/sub 3/; feasibility of high-temperature reference-state thermochemical cycles; interfacing characteristics - solar high-temperature heat sources; analysis of solar and solar hybrid heat sources; and laboratory assessment of cycle with high-temperature step. Engineering analyses were done on two thermochemical hydrogen production cycles - IGT's cycles B-1 and H-5. The load line efficiency for B-1 was 18.1% and for H-5 37.4%. The electrolysis of HBr (aq) on three substrates: platinum, porous graphite, and vitreous graphite was investigated. Platinum proved to be the most efficient electrode surface, with vitreous graphite showing no promise, and porous graphite showing only slightly better results. On platinum, cell voltages of under 1.0 volt were obtained at current densities up to 200 mA/cm/sup 2/. Five new members of the metal-metal oxide class of cycles were derived. The maximum attainable efficiencies of these high-temperature, two-step cycles range from 64 to 86%. Six high-temperature metal oxide-metal sulfate cycles were derived. Performance and capital costs data for a wide range of solar primary heat sources were tabulated.

Hydrolysis of CuCl{sub 2} in the Cu-Cl thermochemical cycle for hydrogen production: Experimental studies using a spray reactor with an ultrasonic atomizer

Energy Technology Data Exchange (ETDEWEB)

Ferrandon, Magali S.; Lewis, Michele A. [Argonne National Laboratory, Chemical Sciences and Engineering Division, 9700 S. Cass Ave., Argonne, IL 60439 (United States); Alvarez, Francisco; Shafirovich, Evgeny [The University of Texas at El Paso, Mechanical Engineering Department, 500 W. University Ave., El Paso, TX 79968 (United States)

2010-03-15

The Cu-Cl thermochemical cycle is being developed as a hydrogen production method. Prior proof-of-concept experimental work has shown that the chemistry is viable while preliminary modeling has shown that the efficiency and cost of hydrogen production have the potential to meet DOE's targets. However, the mechanisms of CuCl{sub 2} hydrolysis, an important step in the Cu-Cl cycle, are not fully understood. Although the stoichiometry of the hydrolysis reaction, 2CuCl{sub 2} + H{sub 2}O <-> Cu{sub 2}OCl{sub 2} + 2HCl, indicates a necessary steam-to-CuCl{sub 2} molar ratio of 0.5, a ratio as high as 23 has been typically required to obtain near 100% conversion of the CuCl{sub 2} to the desired products at atmospheric pressure. It is highly desirable to conduct this reaction with less excess steam to improve the process efficiency. Per Le Chatelier's Principle and according to the available equilibrium-based model, the needed amount of steam can be decreased by conducting the hydrolysis reaction at a reduced pressure. In the present work, the experimental setup was modified to allow CuCl{sub 2} hydrolysis in the pressure range of 0.4-1 atm. Chemical and XRD analyses of the product compositions revealed the optimal steam-to-CuCl{sub 2} molar ratio to be 20-23 at 1 atm pressure. The experiments at 0.4 atm and 0.7 atm showed that it is possible to lower the steam-to-CuCl{sub 2} molar ratio to 15, while still obtaining good yields of the desired products. An important effect of running the reaction at reduced pressure is the significant decrease of CuCl concentration in the solid products, which was not predicted by prior modeling. Possible explanations based on kinetics and residence times are suggested. (author)

Chemical engineering challenges in driving thermochemical hydrogen processes with the tandem mirror reactor

International Nuclear Information System (INIS)

Galloway, T.R.; Werner, R.W.

1980-01-01

The Tandem Mirror Reactor is described and compared with Tokamaks, both from a basic physics viewpoint and from the suitability of the respective reactor for synfuel production. Differences and similarities between the TMR as an electricity producer or a synfuel producer are also cited. The Thermochemical cycle chosen to link with the fusion energy source is the General Atomic Sulfur-Iodine Cycle, which is a purely thermal-driven process with no electrochemical steps. There are real chemical engineering challenges of getting this high quality heat into the large thermochemical plant in an efficient manner. We illustrate with some of our approaches to providing process heat via liquid sodium to drive a 1050 K, highly-endothermic, catalytic and fluidized-bed SO 3 Decomposition Reactor. The technical, economic, and safety tradeoffs that arise are discussed

Thermochemical nitrate reduction

International Nuclear Information System (INIS)

Cox, J.L.; Lilga, M.A.; Hallen, R.T.

1992-09-01

A series of preliminary experiments was conducted directed at thermochemically converting nitrate to nitrogen and water. Nitrates are a major constituent of the waste stored in the underground tanks on the Hanford Site, and the characteristics and effects of nitrate compounds on stabilization techniques must be considered before permanent disposal operations begin. For the thermochemical reduction experiments, six reducing agents (ammonia, formate, urea, glucose, methane, and hydrogen) were mixed separately with ∼3 wt% NO 3 - solutions in a buffered aqueous solution at high pH (13); ammonia and formate were also mixed at low pH (4). Reactions were conducted in an aqueous solution in a batch reactor at temperatures of 200 degrees C to 350 degrees C and pressures of 600 to 2800 psig. Both gas and liquid samples were analyzed. The specific components analyzed were nitrate, nitrite, nitrous oxide, nitrogen, and ammonia. Results of experimental runs showed the following order of nitrate reduction of the six reducing agents in basic solution: formate > glucose > urea > hydrogen > ammonia ∼ methane. Airnmonia was more effective under acidic conditions than basic conditions. Formate was also effective under acidic conditions. A more thorough, fundamental study appears warranted to provide additional data on the mechanism of nitrate reduction. Furthermore, an expanded data base and engineering feasibility study could be used to evaluate conversion conditions for promising reducing agents in more detail and identify new reducing agents with improved performance characteristics

A process for the thermochemical poduction of H2

International Nuclear Information System (INIS)

Norman, J.H.; Russell, J.L. Jr.; Porter, J.T. II; McCorkl, K.H.; Roemer, T.S.; Sharp, Robert.

1976-01-01

A process is described for the thermochemical production of H 2 from water. HI 3 and H 2 SO 4 are prepared by chemical reaction between I 2 , SO 2 and H 2 O. Then HI 3 is heated and decomposed into H 2 and I 2 . The heat is produced by a nuclear reactor [fr

FY 1974 report on the results of the Sunshine Project. R and D of the hydrogen production technology by the thermochemical method; 1974 nendo netsukagakuho ni yoru suiso seizo gijutsu no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1975-05-28

In relation to the R and D of the hydrogen production technology by the thermochemical method, the paper summed up the results of the research conducted in FY 1974. The items for study are as follows. (1) Basic model making for process simulator. (2) Type of facility on the assumption of pilot plant size, and rough selection of equipment structural materials. (3) Extraction of engineering study subjects and working-out of study plans. In (1), the basic model of simulator was established, case studies of various Fe-Cl cycles were made, and a calculation method for the balance of the whole process was established. In (2), it was concluded that in the normal pressure reaction experiment, the oxygen emits extremely little in amount in Mark 9 No. 2 reaction, and therefore, it is very doubtful whether the closed cycle will be completed using this reaction. It was also found out that No. 3 reaction is low in reaction completion degree and it is the problem in point of thermal economy. Accordingly, possibilities of reaction were reviewed, and 6 cycles were found as Fe-Cl cycle. For these reaction cycles, a process flow sheet was made. Comparative studies among processes were conducted, and the cycle structural elementary reaction in Fe-Cl process was specified. (NEDO)

Thermochemical nonequilibrium analysis of O2+Ar based on state-resolved kinetics

International Nuclear Information System (INIS)

Kim, Jae Gang; Boyd, Iain D.

2015-01-01

Highlights: • Thermochemical nonequilibrium studies for three lowest lying electronic states of O 2 . • The complete sets of the rovibrational state-to-state transition rates of O 2 +Ar. • Rovibrational relaxations and coupled chemical reactions of O 2 . • Nonequilibrium reaction rates of O 2 derived from the quasi-steady state assumption. - Abstract: The thermochemical nonequilibrium of the three lowest lying electronic states of molecular oxygen, O 2 (X 3 Σ g - ,a 1 Δ g ,b 1 Σ g + ), through interactions with argon is studied in the present work. The multi-body potential energy surfaces of O 2 +Ar are evaluated from the semi-classical RKR potential of O 2 in each electronic state. The rovibrational states and energies of each electronic state are calculated by the quantum mechanical method based on the present inter-nuclear potential of O 2 . Then, the complete sets of the rovibrational state-to-state transition rate coefficients of O 2 +Ar are calculated by the quasi-classical trajectory method including the quasi-bound states. The system of master equations constructed by the present state-to-state transition rate coefficients are solved to analyze the thermochemical nonequilibrium of O 2 +Ar in various heat bath conditions. From these studies, it is concluded that the vibrational relaxation and coupled chemical reactions of each electronic state needs to be treated as a separate nonequilibrium process, and rotational nonequilibrium needs to be considered at translational temperatures above 10,000 K

Thermochemical Erosion Modeling of the 25-MM M242/M791 Gun System

National Research Council Canada - National Science Library

Sopok, Samuel

1997-01-01

The MACE gun barrel thermochemical erosion modeling code addresses wall degradations due to transformations, chemical reactions, and cracking coupled with pure mechanical erosion for the 25-mm M242/M791 gun system...

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

Science.gov (United States)

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

2018-04-27

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

Thermochemical surface engineering of steels

DEFF Research Database (Denmark)

Thermochemical Surface Engineering of Steels provides a comprehensive scientific overview of the principles and different techniques involved in thermochemical surface engineering, including thermodynamics, kinetics principles, process technologies and techniques for enhanced performance of steels...

Nuclear-produced hydrogen by a thermochemical Cu-Cl plant for passenger hydrogen trains

International Nuclear Information System (INIS)

Marin, G.; Naterer, G.; Gabriel, K.

2010-01-01

This paper compares the technical and economic aspects of electrification of a passenger-train operation in Ontario Canada, versus operation with hydrogen trains using nuclear-produced hydrogen. A local GO Transit diesel operation in Ontario has considered electrification as an alternative to reduce greenhouse gas emissions of passenger trains in the Toronto area. Hydrogen production from nuclear energy via a thermo-chemical Copper-Chlorine (Cu-Cl) cycle for train operation is shown to have lower emissions than direct electrification. It significantly reduces the greenhouse gas emissions compared to diesel operation. A bench-mark reference case used for the nuclear thermo-chemical Cu-Cl cycle is the Sulfur-Iodine (S-I) cycle, under investigation in the USA, Japan, and France, among others. The comparative study in this paper considers a base case of diesel operated passenger trains, within the context of a benefits case analysis for train electrification, for GO Transit operations in Toronto, and the impact of each cost component is discussed. The cost analysis includes projected prices of fuel cell trains, with reference to studies performed by train operators. (author)

Thermodynamic analysis of SCW NPP cycles with thermo-chemical co-generation of hydrogen

International Nuclear Information System (INIS)

Naidin, N.; Mokry, S.; Monichan, R.; Chophla, K.; Pioro, I.; Naterer, G.; Gabriel, K.

2009-01-01

Research activities are currently conducted worldwide to develop Generation IV nuclear reactor concepts with the objective of improving thermal efficiency and increasing economic competitiveness of Generation IV Nuclear Power Plants (NPPs) compared to modern thermal power plants. The Super-Critical Water-cooled Reactor (SCWR) concept is one of the six Generation IV options chosen for further investigation and development in several countries including Canada and Russia. Water-cooled reactors operating at subcritical pressures (10 - 16 MPa) have provided a significant amount of electricity production for the past 50 years. However, the thermal efficiency of the current NPPs is not very high (30 - 35%). As such, more competitive designs, with higher thermal efficiencies, which will be close to that of modern thermal power plants (45 - 50%), need to be developed and implemented. Super-Critical Water (SCW) NPPs will have much higher operating parameters compared to current NPPs (i.e., steam pressures of about 25 MPa and steam outlet temperatures up to 625 o C). Furthermore, SCWRs operating at higher temperatures can facilitate an economical co-generation of hydrogen through thermochemical cycles (particularly, the copper-chlorine cycle) or direct high-temperature electrolysis. The two SCW NPP cycles proposed by this paper are based on direct, regenerative, no-reheat and single-reheat configurations. As such, the main parameters and performance in terms of thermal efficiency of the SCW NPP concepts mentioned above are being analyzed. The cycles are generally comprised of: an SCWR, a SC turbine, one deaerator, ten feedwater heaters, and pumps. The SC turbine of the no-reheat cycle consists of one High-Pressure (HP) cylinder and two Low-Pressure (LP) cylinders. Alternatively, the SC turbine for the single-reheat cycle is comprised of one High-Pressure (HP) cylinder, one Intermediate-Pressure (IP) cylinder and two Low-Pressure (LP) cylinders. Since the single-reheat option

Screening analysis of solar thermochemical hydrogen concepts.

Energy Technology Data Exchange (ETDEWEB)

Diver, Richard B., Jr.; Kolb, Gregory J.

2008-03-01

A screening analysis was performed to identify concentrating solar power (CSP) concepts that produce hydrogen with the highest efficiency. Several CSP concepts were identified that have the potential to be much more efficient than today's low-temperature electrolysis technology. They combine a central receiver or dish with either a thermochemical cycle or high-temperature electrolyzer that operate at temperatures >600 C. The solar-to-hydrogen efficiencies of the best central receiver concepts exceed 20%, significantly better than the 14% value predicted for low-temperature electrolysis.

Thermochemical treatment of radioactive waste by using powder metal fuels

International Nuclear Information System (INIS)

Dmitriev, S.A.; Ojovan, M.I.; Karlina, O.K.

2001-01-01

Full text: A thermochemical approach was suggested for treating and conditioning specific streams of radioactive wastes for example spent ion exchange resins, mixed, organic or chlorine-containing radioactive waste as well as in order to decontaminate heavily contaminated surfaces. Conventional treatment methods of such waste encounters serious problems concerning complete destruction of organic molecules and possible emissions of radionuclides, heavy metals and chemically hazardous species or in case of contaminated materials - complete removal of contamination from surface. The thermochemical treatment of radioactive waste uses powdered metal fuels (PMF) that are specifically formulated for the waste composition and react chemically with the waste components. Thermochemical treatment technologies use the energy of chemical reactions in the mixture of waste with PMF to sustain both decomposition and synthesis processes as well as processes of isomorphic substitutions of hazardous elements into stable mineral forms. The composition of the PMF is designed in such a way as to minimise the release of hazardous components and radionuclides in the off gas and to confine the contaminants in the mineral or glass like final products. The thermochemical procedures allow decomposition of organic matter and capturing hazardous radionuclides and chemical species simultaneously. Thermochemical treatment technologies are very efficient, easy to apply, they have low capital investment and can be used both at large and small facilities. An advantage of thermochemical technologies is their autonomy. Thus these technologies can be successfully applied in order to treat small amount of waste without usage of complex and expensive equipment. They can be used also in emergency situations. Currently the thermochemical treatment technologies were developed and demonstrated to be feasible as follows: 1. Decontamination of surfaces; 2. Processing of organic waste; 3. Vitrification of dusty

Biomass Thermochemical Conversion Program: 1986 annual report

Energy Technology Data Exchange (ETDEWEB)

Schiefelbein, G.F.; Stevens, D.J.; Gerber, M.A.

1987-01-01

Wood and crop residues constitute a vast majority of the biomass feedstocks available for conversion, and thermochemical processes are well suited for conversion of these materials. Thermochemical conversion processes can generate a variety of products such as gasoline hydrocarbon fuels, natural gas substitutes, or heat energy for electric power generation. The US Department of Energy is sponsoring research on biomass conversion technologies through its Biomass Thermochemical Conversion Program. Pacific Northwest Laboratory has been designated the Technical Field Management Office for the Biomass Thermochemical Conversion Program with overall responsibility for the Program. This report briefly describes the Thermochemical Conversion Program structure and summarizes the activities and major accomplishments during fiscal year 1986. 88 refs., 31 figs., 5 tabs.

IS process for thermochemical hydrogen production

International Nuclear Information System (INIS)

Onuki, Kaoru; Nakajima, Hayato; Ioka, Ikuo; Futakawa, Masatoshi; Shimizu, Saburo

1994-11-01

The state-of-the-art of thermochemical hydrogen production by IS process is reviewed including experimental data obtained at JAERI on the chemistry of the Bunsen reaction step and on the corrosion resistance of the structural materials. The present status of laboratory scale demonstration at JAERI is also included. The study on the chemistry of the chemical reactions and the products separations has identified feasible methods to function the process. The flowsheeting studies revealed a process thermal efficiency higher than 40% is achievable under efficient process conditions. The corrosion resistance of commercially available structural materials have been clarified under various process conditions. The basic scheme of the process has been realized in a laboratory scale apparatus. R and D requirements to proceed to the engineering demonstration coupled with HTTR are briefly discussed. (author)

Method for thermochemical decomposition of water

Science.gov (United States)

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.

Conceptual design of SO3 decomposer for thermo-chemical iodine-sulfur process pilot plant

International Nuclear Information System (INIS)

Akihiro Kanagawa; Seiji Kasahara; Atsuhiko Terada; Shinji Kubo; Ryutaro Hino; Yoshiyuki Kawahara; Masaharu Watabe; Hiroshi Fukui; Kazuo Ishino; Toshio Takahashi

2005-01-01

Thermo-chemical water-splitting cycle is a method to make an effective use of the high temperature nuclear heat for hydrogen production. Japan Atomic Energy Research Institute (JAERI) has been conducting R and D on HTGR and also on thermo-chemical hydrogen production by using a thermo-chemical iodine-sulfur cycle (IS process). Based on the test results and know-how obtained through a bench-scale tests of hydrogen production of about 30 NL/hr, JAERI has a plan to construct a pilot test plant heated by high temperature helium gas, which has a hydrogen production performance of 30 Nm 3 /hr and will be operated under the high pressure up to 2 MPa. One of the key components of the pilot test plant is a SO 3 decomposer under high temperature conditions up to 850 degree C and high pressure up to 2 MPa. In this paper, a concept of the SO 3 decomposer for the pilot test plant fabricated with SiC ceramics, a corrosion-resistant material is investigated. Preliminary analyses on temperature and flow-rate distributions in the SO 3 decomposer and on thermal stress were carried out. A SO 3 decomposer model was experimentally manufactured. (authors)

Efficiency of the sulfur–iodine thermochemical water splitting process for hydrogen production based on ADS (accelerator driven system)

International Nuclear Information System (INIS)

García, Lázaro; González, Daniel; García, Carlos; García, Laura; Brayner, Carlos

2013-01-01

The current hydrogen production is based on fossil fuels; they have a huge contribution to the atmosphere's pollution. Thermochemical water splitting cycles don't present this issue because the required process heat is obtained from nuclear energy and therefore, the environmental impact is smaller than using conventional fuels. Although, solar hydrogen production could be also used for practical applications because it's lower environmental impact. One of the promising approaches to produce large quantities of hydrogen in an efficient way using nuclear energy is the sulfur–iodine (S–I) thermochemical water splitting cycle. The nuclear source proposed in this paper is a pebble bed gas cooled transmutation facility. Pebble bed very high temperature advanced systems have great perspectives to assume the future nuclear energy. Softwares based on CPS (chemical process simulation) can be used to simulate the thermochemical water splitting sulfur-iodine cycle for hydrogen production. In this paper, a model for analyzing the sulfur-iodine process sensibility respect to the thermodynamics parameters: temperature, pressure and mass flow is developed. Efficiency is also calculated and the influence of different parameters on this value. The behavior of the proposed model for different values of initial reactant's flow, is analyzed. - Highlights: • Chemical Process Simulation (CPS) of the complete sulfur iodine cycle. • Conceptual design of an accelerator driven system for hydrogen production. • Radial and axial temperature profile for the end of stationary cycle (EOC). • Thermal stability of the sulfuric and hydriodic acid sections determination. • Sulfur iodine cycle efficiency analyses for different heat flow from the ADS

Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

Science.gov (United States)

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.

Cascade enzymatic reactions for efficient carbon sequestration.

Science.gov (United States)

Xia, Shunxiang; Zhao, Xueyan; Frigo-Vaz, Benjamin; Zheng, Wenyun; Kim, Jungbae; Wang, Ping

2015-04-01

Thermochemical processes developed for carbon capture and storage (CCS) offer high carbon capture capacities, but are generally hampered by low energy efficiency. Reversible cascade enzyme reactions are examined in this work for energy-efficient carbon sequestration. By integrating the reactions of two key enzymes of RTCA cycle, isocitrate dehydrogenase and aconitase, we demonstrate that intensified carbon capture can be realized through such cascade enzymatic reactions. Experiments show that enhanced thermodynamic driving force for carbon conversion can be attained via pH control under ambient conditions, and that the cascade reactions have the potential to capture 0.5 mol carbon at pH 6 for each mole of substrate applied. Overall it manifests that the carbon capture capacity of biocatalytic reactions, in addition to be energy efficient, can also be ultimately intensified to approach those realized with chemical absorbents such as MEA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Non-equilibrium thermochemical heat storage in porous media: Part 1 – Conceptual model

International Nuclear Information System (INIS)

Nagel, T.; Shao, H.; Singh, A.K.; Watanabe, N.; Roßkopf, C.; Linder, M.; Wörner, A.; Kolditz, O.

2013-01-01

Thermochemical energy storage can play an important role in the establishment of a reliable renewable energy supply and can increase the efficiency of industrial processes. The application of directly permeated reactive beds leads to strongly coupled mass and heat transport processes that also determine reaction kinetics. To advance this technology beyond the laboratory stage requires a thorough theoretical understanding of the multiphysics phenomena and their quantification on a scale relevant to engineering analyses. Here, the theoretical derivation of a macroscopic model for multicomponent compressible gas flow through a porous solid is presented along with its finite element implementation where solid–gas reactions occur and both phases have individual temperature fields. The model is embedded in the Theory of Porous Media and the derivation is based on the evaluation of the Clausius–Duhem inequality. Special emphasis is placed on the interphase coupling via mass, momentum and energy interaction terms and their effects are partially illustrated using numerical examples. Novel features of the implementation of the described model are verified via comparisons to analytical solutions. The specification, validation and application of the full model to a calcium hydroxide/calcium oxide based thermochemical storage system are the subject of part 2 of this study. - Highlights: • Rigorous application of the Theory of Porous Media and the 2nd law of thermodynamics. • Thermodynamically consistent model for thermochemical heat storage systems. • Multicomponent gas; modified Fick's and Darcy's law; thermal non-equilibrium; solid–gas reactions. • Clear distinction between source and production terms. • Open source finite element implementation and benchmarks

Solar hydrogen project - Thermochemical process design

Energy Technology Data Exchange (ETDEWEB)

Allen, D.J.; Ng, L.F.; Rao, M.S.M.; Wu, S.F.; Zoschak, R.J.

1984-08-01

The thermochemical decomposition of water using solar energy offers an elegant way of combining solar and chemical technologies to produce a high quality fuel. The DOE has sponsored Foster Wheeler to develop a process design for a solar water-splitting process based on the sulfuric acid/iodine cycle. The study has centered around the design of a sulfuric acid decomposition reactor and the central receiver. Materials' properties impose severe constraints upon the design of decomposition reactor. In this paper, the constraints imposed on the design are specified and a reactor and receiver design is presented together with a preliminary design of the balance of plant.

High Efficiency Solar Thermochemical Reactor for Hydrogen Production.

Energy Technology Data Exchange (ETDEWEB)

McDaniel, Anthony H. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

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.

ENERGY EFFICIENCY LIMITS FOR A RECUPERATIVE BAYONET SULFURIC ACID DECOMPOSITION REACTOR FOR SULFUR CYCLE THERMOCHEMICAL HYDROGEN PRODUCTION

Energy Technology Data Exchange (ETDEWEB)

Gorensek, M.; Edwards, T.

2009-06-11

A recuperative bayonet reactor design for the high-temperature sulfuric acid decomposition step in sulfur-based thermochemical hydrogen cycles was evaluated using pinch analysis in conjunction with statistical methods. The objective was to establish the minimum energy requirement. Taking hydrogen production via alkaline electrolysis with nuclear power as the benchmark, the acid decomposition step can consume no more than 450 kJ/mol SO{sub 2} for sulfur cycles to be competitive. The lowest value of the minimum heating target, 320.9 kJ/mol SO{sub 2}, was found at the highest pressure (90 bar) and peak process temperature (900 C) considered, and at a feed concentration of 42.5 mol% H{sub 2}SO{sub 4}. This should be low enough for a practical water-splitting process, even including the additional energy required to concentrate the acid feed. Lower temperatures consistently gave higher minimum heating targets. The lowest peak process temperature that could meet the 450-kJ/mol SO{sub 2} benchmark was 750 C. If the decomposition reactor were to be heated indirectly by an advanced gas-cooled reactor heat source (50 C temperature difference between primary and secondary coolants, 25 C minimum temperature difference between the secondary coolant and the process), then sulfur cycles using this concept could be competitive with alkaline electrolysis provided the primary heat source temperature is at least 825 C. The bayonet design will not be practical if the (primary heat source) reactor outlet temperature is below 825 C.

Efficiency calculations and optimization analysis of a solar reactor for the high temperature step of the zinc/zinc-oxide thermochemical redox cycle

Energy Technology Data Exchange (ETDEWEB)

Haussener, S.

2007-03-15

A solar reactor for the first step of the zinc/zinc-oxide thermochemical redox cycle is analysed and dimensioned in terms of maximization of efficiency and reaction conversion. Zinc-oxide particles carried in an inert carrier gas, in our case argon, enter the reactor in absorber tubes and are heated by concentrated solar radiation mainly due to radiative heat transfer. The particles dissociate and, in case of complete conversion, a gas mixture of argon, zinc and oxygen leaves the reactor. The aim of this study is to find an optimal design of the reactor regarding efficiency, materials and economics. The number of absorber tubes and their dimensions, the cavity dimension and its material as well as the operating conditions should be determined. Therefore 2D and 3D simulations of an 8 kW reactor are implemented. The gases are modeled as ideal gases with temperature-dependent properties. Absorption and scattering of the particle gas mixture are calculated by Mie-theory. Radiative heat transfer is included in the simulation and implemented with the aid of the discrete ordinates (DO) method. The mixture is modeled as ideal mixture and the reaction with an Arrhenius-type ansatz. Temperature distribution, reaction efficiency (heat used for zinc-oxide reaction divided by input) and tube efficiency (heat going into absorber tubes divided by input) as well as reaction conversion are analyzed to find the most promising reactor design. The results show that the most significant factors for efficiencies, conversion and absorber fluid temperature are concentration of the solar incoming radiation, zinc-oxide mass flow, the number of tubes and their dimension. Higher concentration leads to solely positive effects. Zinc-oxide mass flow variations indicate the existence of an optimal flow rate for each reactor design which maximizes efficiencies and conversion. Higher zinc-oxide mass flow leads, on one hand, to higher tube efficiency but on the other hand to lower temperatures in

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

Science.gov (United States)

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.

Hybrid Thermochemical/Biological Processing

Science.gov (United States)

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.

Experimental investigation of molten salt droplet quenching and solidification processes of heat recovery in thermochemical hydrogen production

International Nuclear Information System (INIS)

Ghandehariun, S.; Wang, Z.; Naterer, G.F.; Rosen, M.A.

2015-01-01

Highlights: • Thermal efficiency of a thermochemical cycle of hydrogen production is improved. • Direct contact heat recovery from molten salt is analyzed. • Falling droplets quenched into water are investigated experimentally. - Abstract: This paper investigates the heat transfer and X-ray diffraction patterns of solidified molten salt droplets in heat recovery processes of a thermochemical Cu–Cl cycle of hydrogen production. It is essential to recover the heat of the molten salt to enhance the overall thermal efficiency of the copper–chlorine cycle. A major portion of heat recovery within the cycle can be achieved by cooling and solidifying the molten salt exiting an oxygen reactor. Heat recovery from the molten salt is achieved by dispersing the molten stream into droplets. In this paper, an analytical study and experimental investigation of the thermal phenomena of a falling droplet quenched into water is presented, involving the droplet surface temperature during descent and resulting composition change in the quench process. The results show that it is feasible to quench the molten salt droplets for an efficient heat recovery process without introducing any material imbalance for the overall cycle integration.

Pathways for the release of polonium from a lead-bismuth spallation target (thermochemical calculation); Verfluechtigungspfade des Poloniums aus einem Pb-Bi-Spallationstarget (Thermochemische Kalkulation)

Energy Technology Data Exchange (ETDEWEB)

Eichler, B.; Neuhausen, J

2004-06-01

An analysis of literature data for the thermochemical constants of polonium reveals considerable discrepancies in the relations of these data among each other as well as in their expected trends within the chalcogen group. This fact hinders a reliable assessment of possible reaction paths for the release of polonium from a liquid lead-bismuth spallation target. In this work an attempt is made to construct a coherent data set for the thermochemical properties of polonium and some of its compounds that are of particular importance with respect to the behaviour of polonium in a liquid Pb-Bi target. This data set is based on extrapolations using general trends throughout the periodic table and, in particular, within the chalcogen group. Consequently, no high accuracy should be attributed to the derived data set. However, the data set derived in this work is consistent with definitely known experimental data. Furthermore, it complies with the general trends of physicochemical properties within the chalcogen group. Finally, well known relations between thermochemical quantities are fulfilled by the data derived in this work. Thus, given the lack of accurate experimental data it can be regarded as best available data. Thermochemical constants of polonium hydride, lead polonide and polonium dioxide are derived based on extrapolative procedures. Furthermore, the possibility of formation of the gaseous intermetallic molecule BiPo, which has been omitted from discussion up to now, is investigated. From the derived thermochemical data the equilibrium constants of formation, release and dissociation reactions are calculated for different polonium containing species. Furthermore equilibrium constants are determined for the reaction of lead polonide and polonium dioxide with hydrogen, water vapour and the target components lead and bismuth. The most probable release pathways are discussed. From thermochemical evaluations polonium is expected to be released from liquid lead

Preliminary experimental results of barium chloride-ammonia reaction for using in a solar thermochemical cooling cycle; Resultados experimentales preliminares de la reaccion entre el cloruro de bario y el amoniaco para su utilizacion en un ciclo de refrigeracion solar termoquimico

Energy Technology Data Exchange (ETDEWEB)

Rivera, C. O. B.; Mendez, E. R.; Pilatowsky, L. F.; Rivera, W. G.

2004-07-01

An experimental intermittent thermochemical refrigeration system operating with barium chloride-ammonia reaction is described. The barium chloride is used as absorbent and ammonia as refrigerant. The equipment components and the experimental preliminary results are also presented. The temperature range of the thermal fluid from 70 C to 95 C was established. The main results showed that the generation temperature oscillated from 53 C to 56 C for a condensation temperature of 23 C. The generation pressure range was from 10 to 11 bar. In the evaporating-absorption process, the evaporating temperature range was between 10 C and 0 C for a saturation pressure of 2.4 bar. The results showed also, the technical feasibility to operate this refrigeration system with low cost solar flat plate collectors in remote areas. (Author) CIEMAT (Centro de Investigaciones Energeticas, Mediambientales y Tecnologicas). The LCA is an environmental management methodology with which the environmental impacts associate to a system, process product are detected. The ISO standard 14040: 1997 contain the procedure to follow. life cycle of the plant is divided in 4 stages: extraction and transformation of raw materials; transport and installation; completion of the system to operate like a steam generator maintenance, and dismantling. As result, some improvements are recommended, mainly related to changes in the types of materials and the treatment of the emissions. (Author)

Conceptual design model of the sulfur-iodine S-I thermochemical water splitting process for hydrogen production using nuclear heat source

International Nuclear Information System (INIS)

Gonzalez Rodriguez, Daniel; Parra, Lazaro Garcia

2011-01-01

Hydrogen is the most indicated candidate for its implementation as energy carrier in a future sustainable scenario. The current hydrogen production is based on fossils fuels; they have a huge contribution to the atmosphere pollution. Thermochemical water-splitting cycles do not have this issue because they use solar or nuclear heat; their environment impact is smaller than conventional fuels. The software based on chemical process simulation (CPS) can be used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. In the paper is developed a model for Sulfur-Iodine process in order to analyze his sensibility and calculate the efficiency and the influence of many parameters on this value. (author)

Conceptual design model of the sulfur-iodine S-I thermochemical water splitting process for hydrogen production using nuclear heat source

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Rodriguez, Daniel; Parra, Lazaro Garcia, E-mail: dgr@instec.cu, E-mail: lgarcia@instec.cu [Departamento de Ingenieria Nuclear, Instituto Superior de Ciencias y Tecnologias Aplicadas, La Habana (Cuba)

2011-07-01

Hydrogen is the most indicated candidate for its implementation as energy carrier in a future sustainable scenario. The current hydrogen production is based on fossils fuels; they have a huge contribution to the atmosphere pollution. Thermochemical water-splitting cycles do not have this issue because they use solar or nuclear heat; their environment impact is smaller than conventional fuels. The software based on chemical process simulation (CPS) can be used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. In the paper is developed a model for Sulfur-Iodine process in order to analyze his sensibility and calculate the efficiency and the influence of many parameters on this value. (author)

Achievement report for fiscal 1976 on Sunshine Program. Research and development of hydrogen production technology using thermochemical method; 1976 nendo netsukagakuho ni yoru suiso seizo gijutsu no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1977-03-01

The research and development centers on the details of the Fe-Cu-Cl-based cycle. The items studied in this connection are (1) the development of a process simulator, (2) an experimental study of the Fe-Cu-Cl-based cycle, and (3) the recapitulation of the Fe-Cl-based cycle. The outcome of the comparison of Fe-Cl-based cycles widely conducted in the past enables a conclusion that the Fe-Cu-Cl-based cycle is at present is the most practical, technologically as well as in the way of thermal efficiency. The achievement on the first reaction (hydrolysis of ferrous chloride) of fiscal 1975, and then what is reported in literature on the fifth reaction (reverse Deacon process), are incorporated into the experiment of fiscal 1976, and this completes the acquisition of basic data necessary to develop the Fe-Cu-Cl-based cycle into an application process. Using optimum conditions chosen out of these basic data, a flowchart is compiled and the details of the process are calculated. As the result, a thermal efficiency of 30-33% is obtained, and the figures are deemed to indicate that the thermochemical method is sufficiently superior to the electrolytic method. (NEDO)

Haemolytic activity of uranium compounds haemolysis by thermochemical derivatives of ammonium uranate

International Nuclear Information System (INIS)

Stuart, W.I.; Tucker, A.D.; Adams, R.B.

1975-01-01

A study has been made of the haemolytic action on human erythrocytes by ammonium uranate (AU) and various thermochemical products of AU. These products were obtained by heating AU in hydrogen at 5 0 C min -1 to various temperatures. Haemolysis has been interpreted in terms of a diffusion model which for each product yields a single parameter Ksub(N), the haemolytic activity factor. The magnitude of Ksub(N) is a convenient measure of the ability of a powder to damage erythrocytes. The haemolytic activity of certain thermochemical derivatives indicates an exceptionally high potential for damage to erythrocytes. Infrared and thermoanalytical measurements have shown that the high activity of these products derives principally from a self-reduction reaction, induced by heating AU to 400-420 0 C in hydrogen. (author)

Micro-coulometric study of bioelectrochemical reaction coupled with TCA cycle.

Science.gov (United States)

Tsujimura, Seiya; Fukuda, Jun; Shirai, Osamu; Kano, Kenji; Sakai, Hideki; Tokita, Yuichi; Hatazawa, Tsuyonobu

2012-04-15

The mediated electro-enzymatic electrolysis systems based on the tricarboxylic acid (TCA) cycle reaction were examined on a micro-bulk electrolytic system. A series of the enzyme-catalyzed reactions in the TCA cycle was coupled with electrode reaction. Electrochemical oxidation of NADH was catalyzed by diaphorase with an aid of a redox mediator with a formal potential of -0.15 V vs. Ag|AgCl. The mediator was also able to shuttle electrons between succinate dehydrogenase and electrode. The charge during the electrolysis increased on each addition of dehydrogenase reaction in a cascade of the TCA cycle. However, the electrolysis efficiencies were close to or less than 90% because of the product inhibition. Lactate oxidation to acetyl-CoA catalyzed by two NAD-dependent dehydrogenases was coupled with the bioelectrochemical TCA cycle reaction to achieve the 12-electron oxidation of lactate to CO(2). The charge passed in the bioelectrocatalytic oxidation of 5 nmol of lactate was 4 mC, which corresponds to 70% of the electrolysis efficiency. Copyright © 2012 Elsevier B.V. All rights reserved.

Biomass thermochemical conversion program: 1987 annual report

Energy Technology Data Exchange (ETDEWEB)

Schiefelbein, G.F.; Stevens, D.J.; Gerber, M.A.

1988-01-01

The objective of the Biomass Thermochemical Conversion Program is to generate a base of scientific data and conversion process information that will lead to establishment of cost-effective processes for conversion of biomass resources into clean fuels. To accomplish this objective, in fiscal year 1987 the Thermochemical Conversion Program sponsored research activities in the following four areas: Liquid Hydrocarbon Fuels Technology; Gasification Technology; Direct Combustion Technology; Program Support Activities. In this report an overview of the Thermochemical Conversion Program is presented. Specific research projects are then described. Major accomplishments for 1987 are summarized.

Biomass thermochemical conversion program. 1985 annual report

Energy Technology Data Exchange (ETDEWEB)

Schiefelbein, G.F.; Stevens, D.J.; Gerber, M.A.

1986-01-01

Wood and crop residues constitute a vast majority of the biomass feedstocks available for conversion, and thermochemical processes are well suited for conversion of these materials. The US Department of Energy (DOE) is sponsoring research on this conversion technology for renewable energy through its Biomass Thermochemical Conversion Program. The Program is part of DOE's Biofuels and Municipal Waste Technology Division, Office of Renewable Technologies. This report briefly describes the Thermochemical Conversion Program structure and summarizes the activities and major accomplishments during fiscal year 1985. 32 figs., 4 tabs.

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

Directory of Open Access Journals (Sweden)

Lei Qi

2017-01-01

Full Text Available 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.

Development of a Thermo-chemical Non-equilibrium Solver for Hypervelocity Flows

Science.gov (United States)

Balasubramanian, R.; Anandhanarayanan, K.

2015-04-01

In the present study, a three dimensional flowsolver is indigenously developed to numerically simulate hypervelocity thermal and chemical non equilibrium reactive air flow past flight vehicles. The two-temperature, five species, seventeen reactions, thermo-chemical non equilibrium, non-ionizing, air-chemistry model of Park is implemented in a compressible viscous code CERANS and solved in the finite volume framework. The energy relaxation is addressed by a conservation equation for the vibrational energy of the gas mixture resulting in the evaluation of its vibrational temperature. The AUSM-PW+ numerical flux function has been used for modeling the convective fluxes and a central differencing approximation is used for modeling the diffusive fluxes. The flowsolver had been validated for specifically chosen test cases with inherent flow complexities of non-ionizing hypervelocity thermochemical nonequilibrium flows and results obtained are in good agreement with results available in open literature.

Design of GA thermochemical water-splitting process for the Mirror Advanced Reactor System

International Nuclear Information System (INIS)

Brown, L.C.

1983-04-01

GA interfaced the sulfur-iodine thermochemical water-splitting cycle to the Mirror Advanced Reactor System (MARS). The results of this effort follow as one section and part of a second section to be included in the MARS final report. This section describes the process and its interface to the reactor. The capital and operating costs for the hydrogen plant are described

Benchmarking the DFT+U method for thermochemical calculations of uranium molecular compounds and solids.

Science.gov (United States)

Beridze, George; Kowalski, Piotr M

2014-12-18

Ability to perform a feasible and reliable computation of thermochemical properties of chemically complex actinide-bearing materials would be of great importance for nuclear engineering. Unfortunately, density functional theory (DFT), which on many instances is the only affordable ab initio method, often fails for actinides. Among various shortcomings, it leads to the wrong estimate of enthalpies of reactions between actinide-bearing compounds, putting the applicability of the DFT approach to the modeling of thermochemical properties of actinide-bearing materials into question. Here we test the performance of DFT+U method--a computationally affordable extension of DFT that explicitly accounts for the correlations between f-electrons - for prediction of the thermochemical properties of simple uranium-bearing molecular compounds and solids. We demonstrate that the DFT+U approach significantly improves the description of reaction enthalpies for the uranium-bearing gas-phase molecular compounds and solids and the deviations from the experimental values are comparable to those obtained with much more computationally demanding methods. Good results are obtained with the Hubbard U parameter values derived using the linear response method of Cococcioni and de Gironcoli. We found that the value of Coulomb on-site repulsion, represented by the Hubbard U parameter, strongly depends on the oxidation state of uranium atom. Last, but not least, we demonstrate that the thermochemistry data can be successfully used to estimate the value of the Hubbard U parameter needed for DFT+U calculations.

Generation of H2 and CO by solar thermochemical splitting of H2O and CO2 by employing metal oxides

International Nuclear Information System (INIS)

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

2016-01-01

Generation of H 2 and CO by splitting H 2 O and CO 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 2 O or CO 2 over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H 2 O or CO 2 . While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln 1−x A x Mn 1−y M y O 3 (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H 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 0.5 Sr 0.5 MnO 3 which releases 483 µmol/g of O 2 at 1673 K and produces 757 µmol/g of CO from CO 2 at 1173 K. The production of H 2 from H 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 2 based on the Mn 3 O 4 /NaMnO 2 cycle briefly. - Graphical abstract: Ln 0.5 A 0.5 Mn 1−x M x O 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 2 and H 2 O for the generation of CO and H 2 . - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO 2 and H 2 O. • In Ln 1−x A x MnO 3 perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H 2 O splitting is also achieved by the use of the Mn 3 O 4 -sodium carbonate system. • Thermochemical splitting of CO 2 and H

Thermochemical aspects of fuel-cladding and fuel-coolant interactions in LMFBR oxide fuel pins

International Nuclear Information System (INIS)

Adamson, M.G.; Aitken, E.A.; Caputi, R.W.; Potter, P.E.; Mignanelli, M.A.

1979-01-01

This paper examines several thermochemical aspects of the fuel-cladding, fuel-coolant and fuel-fission product interactions that occur in LMFBR austenitic stainless steel-clad mixed (U,Pu)-oxide fuel pins during irradiation under normal operating conditions. Results are reported from a variety of high temperature EMF cell experiments in which continuous oxygen activity measurements on reacting and equilibrium mixtures of metal oxides and (excess) liquid alkali metal (Na, K, Cs) were performed. Oxygen potential and 0:M thresholds for Na-fuel reactions are re-evaluated in the light of new measurements and newly-assessed thermochemical data, and the influence on oxygen potential of possible U-Pu segregation between oxide and urano-plutonate (equilibrium) phases has been analyzed. (orig./RW) [de

Thermochemical evaluation and preparation of cesium uranates

International Nuclear Information System (INIS)

Takano, Masahide; Minato, Kazuo; Fukuda, Kousaku; Sato, Seichi; Ohashi, Hiroshi.

1997-03-01

Two kinds of cesium uranates, Cs 2 UO 4 and Cs 2 U 2 O 7 , which are predicted by thermochemical estimation to be formed in irradiated oxide fuels, were prepared from U 3 O 8 and Cs 2 CO 3 for measurements of the thermal expansions and thermal conductivities. In advance of the preparation, thermochemical calculations for the formation and decomposition of these cesium uranates were performed by Gibbs free energy minimizer. The preparation temperatures for Cs 2 UO 4 and Cs 2 U 2 O 7 were determined from the results of the thermochemical calculations. The prepared samples were analyzed by X-ray diffraction, which showed that the single phases of Cs 2 UO 4 and Cs 2 U 2 O 7 were formed. Thermogravimetry and differential thermal analysis were also performed on these samples, and the decomposition temperatures were evaluated. The experimental results were in good agreement with those of the thermochemical calculations. (author)

Overview of recent advances in thermo-chemical conversion of biomass

International Nuclear Information System (INIS)

Zhang Linghong; Xu Chunbao; Champagne, Pascale

2010-01-01

Energy from biomass, bioenergy, is a perspective source to replace fossil fuels in the future, as it is abundant, clean, and carbon dioxide neutral. Biomass can be combusted directly to generate heat and electricity, and by means of thermo-chemical and bio-chemical processes it can be converted into bio-fuels in the forms of solid (e.g., charcoal), liquid (e.g., bio-oils, methanol and ethanol), and gas (e.g., methane and hydrogen), which can be used further for heat and power generation. This paper provides an overview of the principles, reactions, and applications of four fundamental thermo-chemical processes (combustion, pyrolysis, gasification, and liquefaction) for bioenergy production, as well as recent developments in these technologies. Some advanced thermo-chemical processes, including co-firing/co-combustion of biomass with coal or natural gas, fast pyrolysis, plasma gasification and supercritical water gasification, are introduced. The advantages and disadvantages, potential for future applications and challenges of these processes are discussed. The co-firing of biomass and coal is the easiest and most economical approach for the generation of bioenergy on a large-sale. Fast pyrolysis has attracted attention as it is to date the only industrially available technology for the production of bio-oils. Plasma techniques, due to their high destruction and reduction efficiencies for any form of waste, have great application potential for hazardous waste treatment. Supercritical water gasification is a promising approach for hydrogen generation from biomass feedstocks, especially those with high moisture contents.

Life cycle assessment of hydrogen production from S-I thermochemical process coupled to a high temperature gas reactor

Energy Technology Data Exchange (ETDEWEB)

Giraldi, M. R.; Francois, J. L.; Castro-Uriegas, D. [Departamento de Sistemas Energeticos, Facultad de Ingenieria, Universidad Nacional Autonoma de Mexico, Paseo Cuauhnahuac No. 8532, Col. Progreso, C.P. 62550, Jiutepec, Morelos (Mexico)

2012-07-01

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 was 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)

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

Science.gov (United States)

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.

Thermochemical and thermophysical properties of minor actinide compounds

International Nuclear Information System (INIS)

Minato, Kazuo; Takano, Masahide; Otobe, Haruyoshi; Nishi, Tsuyoshi; Akabori, Mitsuo; Arai, Yasuo

2009-01-01

Burning or transmutation of minor actinides (MA: Np, Am, Cm) that are classified as the high-level radioactive waste in the current nuclear fuel cycle is an option for the advanced nuclear fuel cycle. Although the thermochemical and thermophysical properties of minor actinide compounds are essential for the design of MA-bearing fuels and analysis of their behavior, the experimental data on minor actinide compounds are limited. To support the research and development of the MA-bearing fuels, the property measurements were carried out on minor actinide nitrides and oxides. The lattice parameters and their thermal expansions were measured by high-temperature X-ray diffractometry. The specific heat capacities were measured by drop calorimetry and the thermal diffusivities by laser-flash method. The thermal conductivities were determined by the specific heat capacities, thermal diffusivities and densities. The oxygen potentials were measured by electromotive force method.

Thermochemical equilibrium modelling of a gasifying process

International Nuclear Information System (INIS)

Melgar, Andres; Perez, Juan F.; Laget, Hannes; Horillo, Alfonso

2007-01-01

This article discusses a mathematical model for the thermochemical processes in a downdraft biomass gasifier. The model combines the chemical equilibrium and the thermodynamic equilibrium of the global reaction, predicting the final composition of the producer gas as well as its reaction temperature. Once the composition of the producer gas is obtained, a range of parameters can be derived, such as the cold gas efficiency of the gasifier, the amount of dissociated water in the process and the heating value and engine fuel quality of the gas. The model has been validated experimentally. This work includes a parametric study of the influence of the gasifying relative fuel/air ratio and the moisture content of the biomass on the characteristics of the process and the producer gas composition. The model helps to predict the behaviour of different biomass types and is a useful tool for optimizing the design and operation of downdraft biomass gasifiers

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-11-01

The results are described of a study of the thermochemical stability of anhydrous uranyl phosphates and arsenates. A number of aspects of chemical technological importance are indicated in detail. The synthesized anhydrous uranyl phosphates and arsenates were very hygroscopic, so that experiments on these compounds had to be carried out under moisture-free conditions. Further characterisation of these compounds are given, including a study of their thermal stabilities and phase relations. The uranyl phosphates reduced reversibly at temperatures of the order of 1100 to 1600 0 C. This makes it possible to express their relative stabilities quantitatively, in terms of the oxygen pressures of the reduction reactions. The thermal decomposition of uranyl arsenates did not occur by reduction, as for the phosphates, but by giving off arsenic oxide vapour. The results of measurements of enthalpies of solution led to the determination of the enthalpies of formation, heat capacity and the standard entropies of the uranyl arsenates. The thermochemical functions at high-temperatures could consequently be calculated. Attention is paid to the possible formation of uranium arsenates, whose uranium has a valency lower than six, hitherto not reported in literature. It was not possible to prepare arsenates of tetravalent uranium. However, three new compounds were observed, one of these, UAsO 5 , was studied in some detail. (Auth.)

Thermo-Chemical Conversion of Microwave Activated Biomass Mixtures

Science.gov (United States)

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.

Thermochemical evaluation and preparation of cesium uranates

Energy Technology Data Exchange (ETDEWEB)

Takano, Masahide; Minato, Kazuo; Fukuda, Kousaku [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Sato, Seichi; Ohashi, Hiroshi

1997-03-01

Two kinds of cesium uranates, Cs{sub 2}UO{sub 4} and Cs{sub 2}U{sub 2}O{sub 7}, which are predicted by thermochemical estimation to be formed in irradiated oxide fuels, were prepared from U{sub 3}O{sub 8} and Cs{sub 2}CO{sub 3} for measurements of the thermal expansions and thermal conductivities. In advance of the preparation, thermochemical calculations for the formation and decomposition of these cesium uranates were performed by Gibbs free energy minimizer. The preparation temperatures for Cs{sub 2}UO{sub 4} and Cs{sub 2}U{sub 2}O{sub 7} were determined from the results of the thermochemical calculations. The prepared samples were analyzed by X-ray diffraction, which showed that the single phases of Cs{sub 2}UO{sub 4} and Cs{sub 2}U{sub 2}O{sub 7} were formed. Thermogravimetry and differential thermal analysis were also performed on these samples, and the decomposition temperatures were evaluated. The experimental results were in good agreement with those of the thermochemical calculations. (author)

Microencapsulation of salts for enhanced thermochemical storage materials

NARCIS (Netherlands)

Cuypers, R.; Jong, A.J. de; Eversdijk, J.; Spijker, J.C. van 't; Oversloot, H.P.; Ingenhut, B.L.J.; Cremers, R.K.H.; Papen-Botterhuis, N.E.

2013-01-01

Thermochemical storage is a new and emerging long-term thermal storage for residential use (cooling, heating & domestic hot water generation), offering high thermal storage density without the need for thermal insulation during storage (Fig. 1). However, existing materials for thermochemical storage

Biomass thermochemical gasification: Experimental studies and modeling

Science.gov (United States)

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

Estimation of formation enthalpies of vanadates by Born-Gaber cycle method

International Nuclear Information System (INIS)

Golovkin, B.G.

1993-01-01

Principle possibility of calculating Gibbs energy of ionic compound formation as a function of thermochemical radii of component ions of temperature and pressure is shown. Formula for determination of thermochemical radii of polyatomic ions is suggested. Enthalpies of formation of 81 vanadates were estimated with the use of Kapustinsky equation and Born-Gaber cycle

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

Science.gov (United States)

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.

From Cycling Between Coupled Reactions to the Cross-Bridge Cycle: Mechanical Power Output as an Integral Part of Energy Metabolism

Directory of Open Access Journals (Sweden)

Frank Diederichs

2012-10-01

Full Text Available ATP delivery and its usage are achieved by cycling of respective intermediates through interconnected coupled reactions. At steady state, cycling between coupled reactions always occurs at zero resistance of the whole cycle without dissipation of free energy. The cross-bridge cycle can also be described by a system of coupled reactions: one energising reaction, which energises myosin heads by coupled ATP splitting, and one de-energising reaction, which transduces free energy from myosin heads to coupled actin movement. The whole cycle of myosin heads via cross-bridge formation and dissociation proceeds at zero resistance. Dissipation of free energy from coupled reactions occurs whenever the input potential overcomes the counteracting output potential. In addition, dissipation is produced by uncoupling. This is brought about by a load dependent shortening of the cross-bridge stroke to zero, which allows isometric force generation without mechanical power output. The occurrence of maximal efficiency is caused by uncoupling. Under coupled conditions, Hill’s equation (velocity as a function of load is fulfilled. In addition, force and shortening velocity both depend on [Ca2+]. Muscular fatigue is triggered when ATP consumption overcomes ATP delivery. As a result, the substrate of the cycle, [MgATP2−], is reduced. This leads to a switch off of cycling and ATP consumption, so that a recovery of [ATP] is possible. In this way a potentially harmful, persistent low energy state of the cell can be avoided.

Thermochemical Surface Engineering: A Playground for Science and Innovation

DEFF Research Database (Denmark)

Christiansen, Thomas Lundin; Dahl, Kristian Vinter; Jellesen, Morten Stendahl

2017-01-01

Surface engineering by thermochemical processing is the intentional change of the composition of a material at elevated temperature with the purpose to improve materials performance. In thermochemical processing components from the starting material are essential in the development of the phases...... at the surface. Current research and innovation activities are used to exemplify thermochemical surface engineering and the interplay of science and innovation. The examples given encompass aspects of the synthesis of extremely porous materials, low temperature surface hardening of stainless steel, surface...

The effects of acute bout of cycling on auditory & visual reaction times.

Science.gov (United States)

Ashnagar, Zinat; Shadmehr, Azadeh; Jalaei, Shohreh

2015-04-01

The purpose of this study was to investigate the effects of an acute bout of cycling exercise on auditory choice reaction time, visual choice reaction time, auditory complex choice reaction time and visual complex choice reaction time. 29 subjects were randomly divided into experimental and control groups. The subjects of the experimental group carried out a single bout of submaximal cycling exercise. The auditory choice reaction time, visual choice reaction time, auditory complex choice reaction time and visual complex choice reaction times were measured before and after the exercise session. The reaction time tests were taken from the subjects by using Speed Anticipation and Reaction Tester (SART) software. In the control group, the reaction time tests were performed by the subjects with an interval of 30 min. In the experimental group, the percentage changes of mean auditory choice and complex choice reaction time values were significantly decreased in comparison with the control group (P visual choice and complex choice reaction times were decreased after the exercise, the changes were not significant (P > 0.05). An acute bout of cycling exercise improved the speed of auditory and visual reaction times in healthy young females. However, these positive changes were significantly observed only in the auditory reaction time tests in comparison with the control group. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermochemical transformations of anthracite fractions

Energy Technology Data Exchange (ETDEWEB)

Belkina, T.V.; Privalov, V.E.; Stepanenko, atM.A.

1979-08-01

Research on the nature of thermochemical transformations of anthracite fractions and the possibility of increasing their activity and identifying conditions for their use in the electrode pitch process is described. From research done on different anthracite fractions processed at varying temperatures it was concluded that accumulations of condensates from heating anthracite fractions occur significantly slower in comparison with pitch. As a result the electrode pitch process is prolonged. Thermal treatment of an anthracite fraction causes the formation and accumulation of condensates and promotes thermochemical transformations. Lastly, the use of thermally treated anthracite fractions apparently intensifies the electrode pitch process and improves its quality. (16 refs.) (In Russian)

Thermochemical heat storage for high temperature applications. A review

Energy Technology Data Exchange (ETDEWEB)

Felderhoff, Michael [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany); Urbanczyk, Robert; Peil, Stefan [Institut fuer Energie- und Umwelttechnik e.V. (IUTA), Duisburg (Germany)

2013-07-01

Heat storage for high temperature applications can be performed by several heat storage techniques. Very promising heat storage methods are based on thermochemical gas solid reactions. Most known systems are metal oxide/steam (metal hydroxides), carbon dioxide (metal carbonates), and metal/hydrogen (metal hydrides) systems. These heat storage materials posses high gravimetric and volumetric heat storage densities and because of separation of the reaction products and their storage in different locations heat losses can be avoided. The reported volumetric heat storage densities are 615, 1340 and 1513 [ kWh m{sup -3}] for calcium hydroxide Ca(OH){sub 2}, calcium carbonate CaCO{sub 3} and magnesium iron hydride Mg{sub 2}FeH{sub 6} respectively. Additional demands for gas storage decrease the heat storage density, but metal hydride systems can use available hydrogen storage possibilities for example caverns, pipelines and chemical plants. (orig.)

A method for carrying out radiolysis and chemical reactions by means of the radiations resulting from a thermonuclear reaction

International Nuclear Information System (INIS)

Gomberg, H.J.

1974-01-01

The invention relates to the use of the radiations resulting from thermonuclear reactions. It deals with a method comprising a combination of thermo-chemical and radiolytic reactions for treating a molecule having a high absorption rate, by the radiations of a thermonuclear reaction. This is applicable to the dissociation of water into oxygen and hydrogen [fr

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

International Nuclear Information System (INIS)

Bennion, Edward P.; Ginosar, Daniel M.; Moses, John; Agblevor, Foster; Quinn, Jason C.

2015-01-01

Highlights: • Well to pump environmental assessment of two thermochemical processing pathways. • NER of 1.23 and GHG emissions of −11.4 g CO 2-eq (MJ) −1 for HTL pathway. • HTL represents promising conversion pathway based on use of wet biomass. • NER of 2.27 and GHG emissions of 210 g CO 2-eq (MJ) −1 for pyrolysis pathway. • Pyrolysis pathway: drying microalgae feedstock dominates environmental impact. - Abstract: Microalgae is being investigated as a renewable transportation fuel feedstock based on various advantages that include high annual yields, utilization of poor quality land, does not compete with food, and can be integrated with various waste streams. This study focuses on directly assessing the environmental impact of two different thermochemical conversion technologies for the microalgae-to-biofuel process through life cycle assessment. A system boundary of “well to pump” (WTP) is defined and includes sub-process models of the growth, dewatering, thermochemical bio-oil recovery, bio-oil stabilization, conversion to renewable diesel, and transport to the pump. Models were validated with experimental and literature data and are representative of an industrial-scale microalgae-to-biofuel process. Two different thermochemical bio-oil conversion systems are modeled and compared on a systems level, hydrothermal liquefaction (HTL) and pyrolysis. The environmental impact of the two pathways were quantified on the metrics of net energy ratio (NER), defined here as energy consumed over energy produced, and greenhouse gas (GHG) emissions. Results for WTP biofuel production through the HTL pathway were determined to be 1.23 for the NER and GHG emissions of −11.4 g CO 2-eq (MJ renewable diesel) −1 . Biofuel production through the pyrolysis pathway results in a NER of 2.27 and GHG emissions of 210 g CO 2-eq (MJ renewable diesel) −1 . The large environmental impact associated with the pyrolysis pathway is attributed to feedstock drying

Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

Institute of Scientific and Technical Information of China (English)

肖圣雄; 张建军; 李旭; 李强国; 任宁; 李环

2010-01-01

A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle ...

Are the lessons of the techno-economic studies on the sulphur-iodine cycle applicable to the other cycles?

International Nuclear Information System (INIS)

Werkoff, F.; Mansilla, C.

2007-01-01

Further advances in nuclear energy system design can broaden the opportunities for the use of nuclear energy. To explore these opportunities, several countries are involved in a forum on the development of next generation nuclear energy systems known as 'Generation IV'. Six concepts have been chosen by the forum, to be studied. The Very High Temperature Reactor (VHTR) offers perspectives for producing electricity and hydrogen with high efficiencies. Nuclear production of hydrogen by thermochemical means is one of the prime candidates for powering the hydrogen economy without producing green house gases. Among them, the Sulphur-Iodine (S-I) thermochemical cycle appeared well fitted with the VHTR, due to the temperature needed for the decomposition of the sulphuric acid. It was invented in the 1970's and it benefits from a revival of interest in the framework of Generation IV. In the last past years, assessments of the S-I process, coupled with a VHTR have been carried out. It appeared that these assessments have to be considered, looking with a particular care to the recommendations of the Generation IV crosscutting economics group [1]: a Generation IV system will: 1. Have a clear life-cost advantage over other energy systems. 2. Have a level of financial risk comparable to other energy projects. The experience gained from techno-economic studies [2, 3] which consider the S-I cycle, indicates that the choice of alternatives cycles to the S-I one must be driven by the characteristic of a previously selected nuclear reactor, mainly the temperature at the nuclear core outlet. Moreover, the net efficiency of the thermochemical cycle must be higher than a reference value defined from the alkaline electrolysis fed by the electricity produced from the selected reactor. Besides, the technical feasibility of the thermochemical processes is not yet established and the production cost of hydrogen from these processes is the result of the sum of several cost factors which are

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

Energy Technology Data Exchange (ETDEWEB)

Yu, Li-Juan; Wan, Wenchao; Karton, Amir, E-mail: amir.karton@uwa.edu.au

2016-11-30

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.

An overview of renewable hydrogen production from thermochemical process of oil palm solid waste in Malaysia

International Nuclear Information System (INIS)

Hosseini, Seyed Ehsan; Wahid, Mazlan Abdul; Ganjehkaviri, A.

2015-01-01

Highlights: • 40% of energy demand of Malaysia could be supplied by thermochemical process of PSR. • SCWG of PSR is preferable thermochemical process due to char and tar elimination. • Potential of H 2 production from SCWG of PSR is 1.05 × 10 10 kgH 2 per year in Malaysia. • Highly moisturized PSR could be used in hydrogen production by SCWG process. - Abstract: Hydrogen is one of the most promising energy carriers for the future of the world due to its tremendous capability of pollution reduction. Hydrogen utilization is free of toxic gases formation as well as carbon dioxide (CO 2 ) emission. Hydrogen production can be implemented using a wide variety of resources including fossil fuels, nuclear energy and renewable and sustainable energy (RSE). Amongst various RSE resources, biomass has great capacity to be employed for renewable hydrogen production. Hydrogen production from palm solid residue (PSR) via thermochemical process is a perfect candidate for waste-to-well strategy in palm oil mills in Malaysia. In this paper, various characteristics of hydrogen production from thermochemical process of PSR includes pyrolysis and gasification are reviewed. The annual oil palm fruits production in Malaysia is approximately 100 million tonnes which the solid waste of the fruits is capable to generate around 1.05 × 10 10 kgH 2 (1.26 EJ) via supercritical water gasification (SCWG) process. The ratio of energy output to energy input of SCWG process of PSR is about 6.56 which demonstrates the priority of SCWG to transform the energy of PSR into a high energy end product. The high moisture of PSR which is the most important barrier for its direct combustion, emerges as an advantage in thermochemical reactions and highly moisturized PSR (even more than 50%) is utilized directly in SCWG without application of any high cost drying process. Implementation of appropriate strategies could lead Malaysia to supply about 40% of its annual energy demand by hydrogen yield from

Estimation of thermochemical behavior of spallation products in mercury target

International Nuclear Information System (INIS)

Kobayashi, Kaoru; Kaminaga, Masanori; Haga, Katsuhiro; Kinoshita, Hidetaka; Aso, Tomokazu; Teshigawara, Makoto; Hino, Ryutaro

2002-02-01

In order to examine the radiation safety of a spallation mercury target system, especially source term evaluation, it is necessary to clarify the chemical forms of spallation products generated by spallation reaction with proton beam. As for the chemical forms of spallation products in mercury that involves large amounts of spallation products, these forms were estimated by using the binary phase diagrams and the thermochemical equilibrium calculation based on the amounts of spallation product. Calculation results showed that the mercury would dissolve Al, As, B, Be, Bi, C, Co, Cr, Fe, Ga, Ge, Ir, Mo, Nb, Os, Re, Ru, Sb, Si, Ta, Tc, V and W in the element state, and Ag, Au, Ba, Br, Ca, Cd, Ce, Cl, Cs, Cu, Dy, Er, Eu, F, Gd, Hf, Ho, I, In, K, La, Li, Lu, Mg, Mn, Na, Nd, Ni, O, Pb, Pd, Pr, Pt, Rb, Rh, S, Sc, Se, Sm, Sn, Sr, Tb, Te, Ti, Tl, Tm, Y, Yb, Zn and Zr in the form of inorganic mercury compounds. As for As, Be, Co, Cr, Fe, Ge, Ir, Mo, Nb, Os, Pt, Re, Ru, Se, Ta, V, W and Zr, precipitation could be occurred when increasing the amounts of spallation products with operation time of the spallation target system. On the other hand, beryllium-7 (Be-7), which is produced by spallation reaction of oxygen in the cooling water of a safety hull, becomes the main factor of the external exposure to maintain the cooling loop. Based on the thermochemical equilibrium calculation to Be-H 2 O binary system, the chemical forms of Be in the cooling water were estimated. Then the Be could exist in the form of cations such as BeOH + , BeO + and Be 2+ under the condition of less than 10 -8 of the Be mole fraction in the cooling water. (author)

[Microcalorimetric determination of thermochemical parameters of the phosphofructokinase reaction].

Science.gov (United States)

Böhme, H J; Schellenberger, W; Hofmann, E

1975-01-01

A calorimetric procedure for determining deltaH, deltaG, deltaS and Keq of a bimolecular reaction with two or more products is described. By using this method the thermodynamic parameters of the phosphofructokinase reaction are determined. At pH 7.0 and 25 degrees C a reaction enthalpy of-6.96kcal/mole was found after correction for the neutralization enthalpy of the buffer and of the enthalpy difference of the magnesium complexes of ATP and ADP, respectively. The free energy of the phosphofructokinase reaction has been found under these conditions to be -3.96kcal/mole.

Advanced construction materials for thermo-chemical hydrogen production from VHTR process heat

International Nuclear Information System (INIS)

Kosmidou, Theodora; Haehner, Peter

2009-01-01

The (very) high temperature reactor concept ((V)HTR) is characterized by its potential for process heat applications. The production of hydrogen by means of thermo-chemical cycles is an appealing example, since it is more efficient than electrolysis due to the direct use of process heat. The sulfur-iodine cycle is one of the best studied processes for the production of hydrogen, and solar or nuclear energy can be used as a heating source for the high temperature reaction of this process. The chemical reactions involved in the cycle are: I 2 (l) + SO 2 (g) +2 H 2 O (l) → 2HI (l) + H 2 SO 4 (l) (70-120 deg. C); H 2 SO 4 (l) → H 2 O (l) + SO 2 (g) + 1/2 O 2 (g) (800-900 deg. C); 2HI (l) → I 2 (g) + H 2 (g) (300-450 deg. C) The high temperature decomposition of sulphuric acid, which is the most endothermic reaction, results in a very aggressive chemical environment which is why suitable materials for the decomposer heat exchanger have to be identified. The class of candidate materials for the decomposer is based on SiC. In the current study, SiC based materials were tested in order to determine the residual mechanical properties (flexural strength and bending modulus, interfacial strength of brazed joints), after exposure to an SO 2 rich environment, simulating the conditions in the hydrogen production plant. Brazed SiC specimens were tested after 20, 100, 500 and 1000 hrs exposure to SO 2 rich environment at 850 o C under atmospheric pressure. The gas composition in the corrosion rig was: 9.9 H 2 O, 12.25 SO 2 , 6.13 O 2 , balance N 2 (% mol). The characterization involved: weight change monitoring, SEM microstructural analysis and four-point bending tests after exposure. Most of the specimens gained weight due to the formation of a corrosion layer as observed in the SEM. The corrosion treatment also showed an effect on the mechanical properties. In the four-point bending tests performed at room temperature and at 850 deg. C, a decrease in bending modulus with

Construction apparatus for thermochemical hydrogen production process

Energy Technology Data Exchange (ETDEWEB)

Kubo, S.; Nakajima, H.; Higashi, S.; Onuki, K.; Akino, S.S.N. [Japan Atomic Energy Research Inst., Ibaraki-ken (Japan). Nuclear Heat Utilization Engineering Lab

2001-06-01

Studies have been carried out at the Japan Atomic Energy Research Institute (JAERI) on hydrogen production through thermochemical processes such as water-splitting. These studies are classified with iodine-sulphur cycle studies using heat from high temperature gas-cooled reactors. An experimental apparatus was constructed with fluorine resin, glass and quartz. It can produce hydrogen at a rate of 50 litres per hour. Electricity provides the heat required for the operation. The closed chemical process requires special control techniques. The process flow diagram for the apparatus was designed based on the results of previous studies including one where hydrogen production was successfully achieved at a rate of one liter per hour for 48 hours. Experimental operations under atmospheric pressure will be carried out for the next four years to develop the process. The data will be used in the next research and development programs aimed at designing a bench-scale apparatus. 7 refs., 1 tab., 8 figs.

Sulfur Based Thermochemical Heat Storage for Baseload Concentrated Solar Power Generation

Energy Technology Data Exchange (ETDEWEB)

Wong, Bunsen [General Atomics, San Diego, CA (United States)

2014-11-01

This project investigates the engineering and economic feasibility of supplying baseload power using a concentrating solar power (CSP) plant integrated with sulfur based thermochemical heat storage. The technology stores high temperature solar heat in the chemical bonds of elemental sulfur. Energy is recovered as high temperature heat upon sulfur combustion. Extensive developmental and design work associated with sulfur dioxide (SO₂) disproportionation and sulfuric acid (H₂SO₄) decomposition chemical reactions used in this technology had been carried out in the two completed phases of this project. The feasibility and economics of the proposed concept was demonstrated and determined.

OPTIMIZED WTE CONVERSION OF MUNICIPAL SOLID WASTE IN SHANGHAI APPLYING THERMOCHEMICAL TECHNOLOGIES

OpenAIRE

Dai, Siyang

2016-01-01

Thermochemical technologies have been proven effective in treating municipal solid waste (MSW) for many years. China, with a rapid increase of MSW, plans to implement more environmental friendly ways to treat MSW than landfill, which treats about 79 % of total MSW currently. The aim of this master thesis was to find out a suitable thermochemical technology to treat MSW in Shanghai, China. Several different thermochemical technologies are compared in this thesis and plasma gasification was sel...

Achievement report on research and development in the Sunshine Project in fiscal 1980. Research on a hydrogen manufacturing technology by using thermo-chemical method. (Research on equipment materials for iodine system cycle); 1980 nendo netsukagakuho ni yoru suiso seizo gijutsu no kenkyu seika hokokusho. Yosokei cycle no sochi zairyo no kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-03-01

This paper describes research on materials of equipment for the second stage reaction in relation with development on a hydrogen manufacturing technology by using the iodine system cycle in the thermo-chemical method. The second stage reaction produces MgO, I{sub 2} and O{sub 2} by decomposition of Mg(IO{sub 3}){sub 2} at 600 to 650 degrees C. Corrosion tests were carried out by using 25Cr-20Ni steel and Ni-50Cr alloy having shown relatively high corrosion resistance in the researches to date, which were added with trace amount of different alloy elements. The tests were performed in gas mixture of I{sub 2}, O{sub 2} and H{sub 2}O at 600 to 700 degrees C for 48 to 192 hours. The average corrosion rate of 25Cr-20Ni steel was reduced by adding Y(0.2%), Ca (0.2%) or Si+Al (1%Si+1%Al), by which relatively uniform corrosion pattern was shown, and the corrosion resistance was improved remarkably. The average corrosion rate of 25Cr-20Ni steel showed a trend of increasing by adding Si and Nb, and non-uniform corrosion like pitting has occurred, revealing that it is not preferable from the aspect of corrosion resistance. The average corrosion rates of the tested materials tended to become somewhat greater under heat insulated condition than under continuously heating condition. Effect of Mg(IO{sub 3}){sub 2} deposition is very small. (NEDO)

Generation of H{sub 2} and CO by solar thermochemical splitting of H{sub 2}O and CO{sub 2} by employing metal oxides

Energy Technology Data Exchange (ETDEWEB)

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

2016-10-15

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 of 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

Thermochemical storage for CSP via redox structured reactors/heat exchangers: The RESTRUCTURE project

Science.gov (United States)

Karagiannakis, George; Pagkoura, Chrysoula; Konstandopoulos, Athanasios G.; Tescari, Stefania; Singh, Abhishek; Roeb, Martin; Lange, Matthias; Marcher, Johnny; Jové, Aleix; Prieto, Cristina; Rattenbury, Michael; Chasiotis, Andreas

2017-06-01

The present work provides an overview of activities performed in the framework of the EU-funded collaborative project RESTRUCTURE, the main goal of which was to develop and validate a compact structured reactor/heat exchanger for thermochemical storage driven by 2-step high temperature redox metal oxide cycles. The starting point of development path included redox materials qualification via both theoretical and lab-scale experimental studies. Most favorable compositions were cobalt oxide/alumina composites. Preparation of small-scale structured bodies included various approaches, ranging from perforated pellets to more sophisticated honeycomb geometries, fabricated by extrusion and coating. Proof-of-concept of the proposed novel reactor/heat exchanger was successfully validated in small-scale structures and the next step included scaling up of redox honeycombs production. Significant challenges were identified for the case of extruded full-size bodies and the final qualified approach related to preparation of cordierite substrates coated with cobalt oxide. The successful experimental evaluation of the pilot reactor/heat exchanger system constructed motivated the preliminary techno-economic evaluation of the proposed novel thermochemical energy storage concept. Taking into account experimental results, available technologies and standard design aspects a model for a 70.5 MWe CSP plant was defined. Estimated LCOE costs were calculated to be in the range of reference values for Combined Cycle Power Plants operated by natural gas. One of main cost contributors was the storage system itself, partially due to relatively high cost of cobalt oxide. This highlighted the need to identify less costly and equally efficient to cobalt oxide redox materials.

Integrated gasification and Cu-Cl cycle for trigeneration of hydrogen, steam and electricity

Energy Technology Data Exchange (ETDEWEB)

Aghahosseini, S; Dincer, I; Naterer, G F [University of Ontario, Oshawa, ON (Canada). Institute of Technology

2011-02-15

This paper develops and analyzes an integrated process model of an Integrated Gasification Combined Cycle (IGCC) and a thermochemical copper-chlorine (Cu-Cl) cycle for trigeneration of hydrogen, steam and electricity. The process model is developed with Aspen HYSYS software. By using oxygen instead of air for the gasification process, where oxygen is provided by the integrated Cu-Cl cycle, it is found that the hydrogen content of produced syngas increases by about 20%, due to improvement of the gasification combustion efficiency and reduction of syngas NOx emissions. Moreover, about 60% of external heat required for the integrated Cu-Cl cycle can be provided by the IGCC plant, with minor modifications of the steam cycle, and a slight decrease of IGCC overall efficiency. Integration of gasification and thermochemical hydrogen production can provide significant improvements in the overall hydrogen, steam and electricity output, when compared against the processes each operating separately and independently of each other.

Li depletion effects on Li2TiO3 reaction with H2 in thermo-chemical environment relevant to breeding blanket for fusion power plants

International Nuclear Information System (INIS)

Alvani, Carlo; Casadio, Sergio; Contini, Vittoria; Giorgi, Rossella; Mancini, Maria Rita; Tsuchiya, Kunihiko; Kawamura, Hiroshi

2005-07-01

This is a report of the Working Group in the Subtask on Solid Breeder Blankets under the Implementing Agreement on a Co-operative Programme on Nuclear Technology of Fusion Reactors (International Energy Agency (IEA)). This Working Group (Task F and WG-F) was performed from 2000 to 2004 by a collaboration of European Union (EU) and Japan (JA). In this report, lithium depletion effects on the reaction of lithium titanate (Li 2 TiO 3 ) with hydrogen (H 2 ) in thermo-chemical environment were discussed. The reaction of Li 2 TiO 3 ceramics with H 2 was studied in a thermo-chemical environment simulating (excepting irradiation) that of the hottest pebble-bed zone of breeding-blanket actually designed for fusion power plants. This 'reduction' as performed at 900degC in Ar+0.1%H, purge gas (He+0.1%H 2 being the designed reference') was found to be enhanced by TiO 2 doping of the specimens of simulate 6 Li-burn-up expected to reach 20% at their end-of-life. The reaction rates, however, were so slow to be not significantly extrapolated to the breeder material service time (years). In Ar+3%H 2 , faster reaction rates allowed a better identification of the process evolution (kinetics) by Temperature-Programmed Reduction' (TPR) and 'Oxidation' (TPO), and combined TG-DTA thermal analysis. The reduction of pure Li 4/5 TiO 12/5 spinel phase to Li 4/5 TiO 12/5-y was found to reach in one day the steady state at the O-vacancy concentration y=0.2. Complimentary microscopy (SEM) and spectroscopy (XRD, XPS) techniques were used to characterize the reaction products among which the presence of the orthorhombic Li v TiO 2 (0 ≤ v ≤ 1/2) and Li 2 TiO 3 could be diagnosed. So that the complete spinel reduction to Li 1/2 TiO 2 was obtained according to a scheme involving the Li 1/2 TiO 2 -Li 4/5 TiO 12/5 spinel phase solid solution for which y=3v/(10-5v). The reduction rate of pure meta-titanate to Li 2 TiO 3-x was found much lower (x approx. = 0.01) and even possibly due to the presence

Energetic optimization of a solar thermochemical energy storage system subject to real constraints

Energy Technology Data Exchange (ETDEWEB)

Lovegrove, K [Australian National Univ., Canberra (Australia). Energy Research Centre

1993-12-01

An approach to the optimization of a solar energy conversion system which involves treating the system as a series of subsystems, each having a single cost determining variable, is proposed. The application to an ammonia-based thermochemical system with direct work output is discussed and possible subsystems are identified. The subsystem consisting of the exothermic reactor has been studied in detail. For this subsystem, the ratio of available catalyst volume to thermal power level is held constant whilst the exergetic efficiency is maximized. Results are presented from a determination of optimized reaction paths using dynamic programming techniques. (author)

Computer-assisted evaluation of the thermochemical data of the compounds of thorium

International Nuclear Information System (INIS)

Wagman, D.D.; Schumm, R.H.; Parker, V.B.

1977-08-01

Selected values are given for the thermochemical properties of the compounds of thorium. They are obtained from a computer-assisted least sums-least squares approach to the evaluation of thermodynamic data networks. The properties given, where data are available, are enthalpy of formation, Gibbs energy of formation, and entropy at 298.15 K (Δ Hf (298), Δ Gf (298), and S (298)). The values are consistent with the CODATA Key Values for Thermodynamics. The reaction catalog from which this self consistent set of values is generated is given with a statistical analysis. Some thermal functions are also given, as well as detailed comments when necessary

Thermochemical Biomass Gasification: A Review of the Current Status of the Technology

Directory of Open Access Journals (Sweden)

Ajay Kumar

2009-07-01

Full Text Available A review was conducted on the use of thermochemical biomass gasification for producing biofuels, biopower and chemicals. The upstream processes for gasification are similar to other biomass processing methods. However, challenges remain in the gasification and downstream processing for viable commercial applications. The challenges with gasification are to understand the effects of operating conditions on gasification reactions for reliably predicting and optimizing the product compositions, and for obtaining maximal efficiencies. Product gases can be converted to biofuels and chemicals such as Fischer-Tropsch fuels, green gasoline, hydrogen, dimethyl ether, ethanol, methanol, and higher alcohols. Processes and challenges for these conversions are also summarized.

Thermochemical data for reactor materials and fission products: The ECN database

International Nuclear Information System (INIS)

Cordfunke, E.H.P.; Konings, R.J.M.

1993-02-01

The activities of the authors regarding the compilation of a database of thermochemical properties for reactor materials and fission products is reviewed. The evaluation procedures and techniques are outlined and examples are given. In addition, examples of the use of thermochemical data for the application in the field of Nuclear Technology are given. (orig.)

Explaining the Stock Market's Reaction to Unemployment News Over the Business Cycle

NARCIS (Netherlands)

Driessen, Joost; Kuiper, Ivo

This paper analyzes the impact of unemployment news on stock markets throughout the business cycle. We show dependence of the reaction to the economic environment by studying the reaction in multiple economic environments that are defined based on both the level and momentum of economic activity.

A thermodynamic and kinetic study of the de- and rehydration of Ca(OH){sub 2} at high H{sub 2}O partial pressures for thermo-chemical heat storage

Energy Technology Data Exchange (ETDEWEB)

Schaube, F.; Koch, L. [German Aerospace Center, Institute of Technical Thermodynamics, Pfaffenwaldring 38-40, 70569 Stuttgart (Germany); Woerner, A., E-mail: antje.woerner@dlr.de [German Aerospace Center, Institute of Technical Thermodynamics, Pfaffenwaldring 38-40, 70569 Stuttgart (Germany); Mueller-Steinhagen, H. [German Aerospace Center, Institute of Technical Thermodynamics, Pfaffenwaldring 38-40, 70569 Stuttgart (Germany)

2012-06-20

Highlights: Black-Right-Pointing-Pointer Investigation of the thermodynamic equilibrium and reaction enthalpy of 'Ca(OH){sub 2} {r_reversible} CaO + H{sub 2}O'. Black-Right-Pointing-Pointer Investigation of the reaction kinetics of the dehydration of Ca(OH){sub 2} at partial pressures up to 956 mbar. Black-Right-Pointing-Pointer Investigation of the reaction kinetics of the rehydration of Ca(OH){sub 2} at partial pressures up to 956 mbar. - Abstract: Heat storage technologies are used to improve energy efficiency of power plants and recovery of process heat. Storing thermal energy by reversible thermo-chemical reactions offers a promising option for high storage capacities especially at high temperatures. Due to its low material cost, the use of the reversible reaction Ca(OH){sub 2} Rightwards-Harpoon-Over-Leftwards-Harpoon CaO + H{sub 2}O has been proposed. This paper reports on the physical properties such as heat capacity, thermodynamic equilibrium, reaction enthalpy and kinetics. To achieve high reaction temperatures, high H{sub 2}O partial pressures are required. Therefore the cycling stability is confirmed for H{sub 2}O partial pressures up to 95.6 kPa and the dehydration and hydration kinetics are studied. Quantitative data are collected and expressions are derived which are in good agreement with the presented measurements. At 1 bar H{sub 2}O partial pressure the expected equilibrium temperature is 505 Degree-Sign C and the reaction enthalpy is 104.4 kJ/mol.

2009 Thermochemical Conversion Platform Review Report

Energy Technology Data Exchange (ETDEWEB)

Ferrell, John [Office of Energy Efficiency and Renewable Energy (EERE), Washington, DC (United States)

2009-12-01

This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the U.S. Department of Energy Biomass Program’s Thermochemical Conversion platform review meeting, held on April 14-16, 2009, at the Sheraton Denver Downtown, Denver, Colorado.

Achievement report on research and development in the Sunshine Project in fiscal 1978. Research and development of hydrogen manufacturing technologies using the thermo-chemical method; 1978 nendo netsukagakuho ni yoru suiso seizo gijutsu no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1979-05-31

This paper describes a summary design of an iodine cycle experimenting equipment as one of the achievements in fiscal 1978 on research of hydrogen manufacturing technologies using the thermo-chemical method. The object of the equipment is a reaction to derive Mg(IO{sub 3}){sub 2} and MgI{sub 2} from MgO being the first reaction of the cycle, and iodine. The by-product (Q-phase) is produced according to composition of the aqueous reaction solution. The occurring reaction and composition of the produced materials vary depending on which contact system the reactor type uses, countercurrent flow or concurrent flow. Discussions were given on both types. Hydrogen generation rate of 1 Nm{sup 3}/hr was assumed as the equipment size to derive material balance and heat balance. Furthermore, types considered applicable were selected from different types of the solid-liquid reaction equipment, and summary design and calculation were performed. Process simulation provided a prospect of achieving thermal efficiency that can compete with the electrolytic process. As a study on materials for a magnesium iodate pyrolytic equipment as the second reaction, corrosion tests were carried out in a gas mixture composed of iodine, oxygen and steam. Using 26 kinds of metallic materials as the objects, the tests were executed at 100 and 300 degrees C for 100 hours. Long-term durability tests were also performed on materials judged to have good corrosion resistance. (NEDO)

Thermochemical ablation therapy of VX2 tumor using a permeable oil-packed liquid alkali metal.

Directory of Open Access Journals (Sweden)

Ziyi Guo

Full Text Available Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors.Permeable oil-packed sodium-potassium (NaK was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E. staining.The injection of the NaK-oil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaK-oil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors.The NaK-oil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors.

Estimation of thermochemical behavior of spallation products in mercury target

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, Kaoru; Kaminaga, Masanori; Haga, Katsuhiro; Kinoshita, Hidetaka; Aso, Tomokazu; Teshigawara, Makoto; Hino, Ryutaro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

2002-02-01

In order to examine the radiation safety of a spallation mercury target system, especially source term evaluation, it is necessary to clarify the chemical forms of spallation products generated by spallation reaction with proton beam. As for the chemical forms of spallation products in mercury that involves large amounts of spallation products, these forms were estimated by using the binary phase diagrams and the thermochemical equilibrium calculation based on the amounts of spallation product. Calculation results showed that the mercury would dissolve Al, As, B, Be, Bi, C, Co, Cr, Fe, Ga, Ge, Ir, Mo, Nb, Os, Re, Ru, Sb, Si, Ta, Tc, V and W in the element state, and Ag, Au, Ba, Br, Ca, Cd, Ce, Cl, Cs, Cu, Dy, Er, Eu, F, Gd, Hf, Ho, I, In, K, La, Li, Lu, Mg, Mn, Na, Nd, Ni, O, Pb, Pd, Pr, Pt, Rb, Rh, S, Sc, Se, Sm, Sn, Sr, Tb, Te, Ti, Tl, Tm, Y, Yb, Zn and Zr in the form of inorganic mercury compounds. As for As, Be, Co, Cr, Fe, Ge, Ir, Mo, Nb, Os, Pt, Re, Ru, Se, Ta, V, W and Zr, precipitation could be occurred when increasing the amounts of spallation products with operation time of the spallation target system. On the other hand, beryllium-7 (Be-7), which is produced by spallation reaction of oxygen in the cooling water of a safety hull, becomes the main factor of the external exposure to maintain the cooling loop. Based on the thermochemical equilibrium calculation to Be-H{sub 2}O binary system, the chemical forms of Be in the cooling water were estimated. Then the Be could exist in the form of cations such as BeOH{sup +}, BeO{sup +} and Be{sup 2+} under the condition of less than 10{sup -8} of the Be mole fraction in the cooling water. (author)

Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

International Nuclear Information System (INIS)

Zamfirescu, C.; Naterer, G.F.; Dincer, I.

2009-01-01

The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

Review of the direct thermochemical conversion of lignocellulosic biomass for liquid fuels

Directory of Open Access Journals (Sweden)

Jianchun JIANG,Junming XU,Zhanqian SONG

2015-03-01

Full Text Available Increased demand for liquid transportation fuels, environmental concerns and depletion of petroleum resources requires the development of efficient conversion technologies for production of second-generation biofuels from non-food resources. Thermochemical approaches hold great potential for conversion of lignocellulosic biomass into liquid fuels. Direct thermochemical processes convert biomass into liquid fuels in one step using heat and catalysts and have many advantages over indirect and biological processes, such as greater feedstock flexibility, integrated conversion of whole biomass, and lower operation costs. Several direct thermochemical processes are employed in the production of liquid biofuels depending on the nature of the feedstock properties: such as fast pyrolysis/liquefaction of lignocellulosic biomass for bio-oil, including upgrading methods, such as catalytic cracking and hydrogenation. Owing to the substantial amount of liquid fuels consumed by vehicular transport, converting biomass into drop-in liquid fuels may reduce the dependence of the fuel market on petroleum-based fuel products. In this review, we also summarize recent progress in technologies for large-scale equipment for direct thermochemical conversion. We focus on the technical aspects critical to commercialization of the technologies for production of liquid fuels from biomass, including feedstock type, cracking catalysts, catalytic cracking mechanisms, catalytic reactors, and biofuel properties. We also discuss future prospects for direct thermochemical conversion in biorefineries for the production of high grade biofuels.

Thermo effect of chemical reaction in irreversible electrochemical systems

International Nuclear Information System (INIS)

Tran Vinh Quy; Nguyen Tang

1989-01-01

From first law of thermodynamics the expressions of statistical calculation of 'Fundamental' and 'Thermo-chemical' thermal effects are obtained. Besides, method of calculation of thermal effect of chemical reactions in non-equilibrium electro-chemical systems is accurately discussed. (author). 7 refs

Performance analysis of a photovoltaic-thermochemical hybrid system prototype

International Nuclear Information System (INIS)

Li, Wenjia; Ling, Yunyi; Liu, Xiangxin; Hao, Yong

2017-01-01

Highlights: •A modular photovoltaic-thermochemical hybrid system prototype is proposed. •Net solar-electric efficiency up to 41% is achievable. •Stable solar power supply is achievable via convenient energy storage. •The modular design facilitates the scalability of the hybrid system. -- Abstract: A solar photovoltaic (PV) thermochemical hybrid system consisting of a point-focus Fresnel concentrator, a PV cell and a methanol thermochemical reactor is proposed. In particular, a reactor capable of operating under high solar concentration is designed, manufactured and tested. Studies on both kinetic and thermodynamic characteristics of the reactor and the system are performed. Analysis of numerical and experimental results shows that with cascaded solar energy utilization and synergy among different forms of energy, the hybrid system has the advantages of high net solar-electric efficiency (up to 41%), stable solar energy power supply, solar energy storage (via syngas) and flexibility in application scale. The hybrid system proposed in this work provides a potential solution to some key challenges of current solar energy utilization technologies.

Hydrogen production using the sulfur-iodine cycle coupled to a VHTR: An overview

International Nuclear Information System (INIS)

Vitart, X.; Le Duigou, A.; Carles, P.

2006-01-01

The sulfur-iodine thermo-chemical cycle is considered to be one of the most promising routes for massive hydrogen production, using high temperature heat from a Generation IV VHTR. We propose here a brief overview of the main questions raised by this cycle, along with the general lines of French CEA's program

Research and development on chemical reactors made of industrial structural materials and hydriodic acid concentration technique for thermochemical hydrogen production IS process

International Nuclear Information System (INIS)

Kubo, Shinji; Iwatsuki, Jin; Takegami, Hiroaki; Kasahara, Seiji; Tanaka, Nobuyuki; Noguchi, Hiroki; Kamiji, Yu; Onuki, Kaoru

2015-10-01

Japan Atomic Energy Agency has been conducting a study on IS process for thermochemical hydrogen production in order to develop massive hydrogen production technology for hydrogen society. Integrity of the chemical reactors and concentration technology of hydrogen iodide in HIx solution were studied. In the former study, the chemical reactors were trial-fabricated using industrial materials. A test of 30 times of thermal cycle test under circulating condition of the Bunsen reaction solution showed integrity of the Bunsen reactor made of fluororesin lined steel. Also, 100 hours of reaction tests showed integrity of the sulfuric acid decomposer made of silicon carbide and of the hydrogen iodide decomposer made of Hastelloy C-276. In the latter study, concerning electro-electrodialysis using cation-exchange membrane, sulfuric acid in the anolyte had little influence on the concentration performance. These results suggest the purification system of HIx solution can be simplified. Based on the Nernst-Planck equation and the Smoluchowski equation, proton transport number, water permeance, and IR drop of the cation exchange membrane were formulated. The derived equations enable quantitative estimation for the performance indexes of Nafion ® membrane and, also, of ETFE-St membranes made by radiation-induced graft polymerization method. (author)

Measurement of proton capture reactions in the hot cycles: an evaluation of experimental methods

Energy Technology Data Exchange (ETDEWEB)

Leleux, P [Inst. de Physique Nucleaire, Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium)

1998-06-01

In the hot cycles, most of the proton capture reactions involve radioactive nuclei in the entrance and exit channels. This paper evaluates the specific methods that were designed to measure such reactions. (orig.)

Extension of a reactive distillation process design methodology: application to the hydrogen production through the Iodine-Sulfur thermochemical cycle; Generalisation d'une approche de conception de procedes de distillation reactive: application a la production d'hydrogene par le cycle thermochimique I-S

Energy Technology Data Exchange (ETDEWEB)

Belaissaoui, B

2006-02-15

Reactive distillation is a promising way to improve classical processes. This interest has been comforted by numerous successful applications involving reactive systems in liquid phase but never in vapour phase. In this context, general design tools have been developed for the analysis of reactive distillation processes whatever the reactive phase. A general model for open condensation and evaporation of vapour or liquid reactive systems in chemical equilibrium has been written and applied to extend the feasibility analysis, synthesis and design methods of the sequential design methodology of R. Thery (2002). The extended design methodology is applied to the industrial production of hydrogen through the iodine-sulphur thermochemical cycle by vapour phase reactive distillation. A column configuration is proposed with better performance formerly published configuration. (author)

Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

International Nuclear Information System (INIS)

Hafsteinsdottir, Erla G.; White, Duanne A.; Gore, Damian B.; Stark, Scott C.

2011-01-01

Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H 2 PO 4 ) 2 ] or sodium phosphate [Na 3 PO 4 ]) reacts with lead (PbSO 4 or PbCl 2 ) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO 4 and Na 3 PO 4 were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: → Formation of lead phosphate products in cold environments is identified. → Potential change in formation during freeze-thaw cycling is assessed. → Lead phosphate reaction efficiency varies according to phosphate and lead source. → Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

OECD/NEA thermochemical database

Energy Technology Data Exchange (ETDEWEB)

Byeon, Kee Hoh; Song, Dae Yong; Shin, Hyun Kyoo; Park, Seong Won; Ro, Seung Gy

1998-03-01

This state of the art report is to introduce the contents of the Chemical Data-Service, OECD/NEA, and the results of survey by OECD/NEA for the thermodynamic and kinetic database currently in use. It is also to summarize the results of Thermochemical Database Projects of OECD/NEA. This report will be a guide book for the researchers easily to get the validate thermodynamic and kinetic data of all substances from the available OECD/NEA database. (author). 75 refs.

Final Report UCLA-Thermochemical Storage with Anhydrous Ammonia

Energy Technology Data Exchange (ETDEWEB)

Lavine, Adrienne [Univ. of California, Los Angeles, CA (United States)

2018-02-05

associated with storage of gas phase components. 3. While this project is primarily concerned with high-temperature heat recovery and methods to store the gaseous components, it is also important to consider the feasibility of the entire system. Consequently, an additional goal was to perform analysis to show the feasibility of integrating endothermic reactors within a tower receiver. A conceptual design of an ammonia dissociation receiver/reactor has been developed that fits into the same size cylindrical envelope as the molten salt receiver in SAM, and has the same design thermal capacity. The calculated thermal efficiency of this receiver is 94.6%. Thus, this investigation has established the technical feasibility of a surround field tower system using ammonia dissociation. With these challenges addressed, we proceeded to design a full-scale synthesis and heat recovery system. A model was developed and validated by comparison with our experimental data. A parametric study showed, among other things, the importance of using small tube diameters and spacing to enhance heat transfer. Multi-parameter optimization was used to find a design that minimizes the wall material volume. Finally, cost estimation shows that the ammonia system has good prospects of meeting the Sunshot 15(USD)/kWht target: estimated costs of the entire synthesis system for the 220 MWt plant with 6 hours of storage are 13(USD)/kWht using salt cavern storage and 18(USD)/kWht using shaft drilling. Costs per kWht are even lower with more hours of storage. With the established technology of ammonia synthesis as a starting point, the successes of the project have mitigated technical risks associated with high-temperature synthesis reaction, underground storage, and tower receiver design. Estimated costs are less than 15(USD)/kWht with salt cavern storage. It is now possible to map a time line to commercial deployment that is likely to be shorter and less risky than other thermochemical cycles under active

Multi-state system in a fault tree analysis of a nuclear based thermochemical hydrogen plant

International Nuclear Information System (INIS)

Zhang, Y.

2008-01-01

Nuclear-based hydrogen generation is a promising way to supply hydrogen for this large market in the future. This thesis focuses on one of the most promising methods, a thermochemical Cu-Cl cycle, which is currently under development by UOIT, Atomic Energy of Canada Limited (AECL) and the Argonne National Laboratory (ANL). The safety issues of the Cu-Cl cycle are addressed in this thesis. An investigation of major accident scenarios shows that potential tragedies can be avoided with effective risk analysis and safety management programs. As a powerful and systematic tool, fault tree analysis (FTA) is adapted to the particular needs of the Cu-Cl system. This thesis develops a new method that combines FTA with a reliability analysis tool, multi-state system (MSS), to improve the accuracy of FTA and also improve system reliability. (author)

The uranium-carbon and plutonium-carbon systems. A thermochemical assessment

International Nuclear Information System (INIS)

1963-01-01

A fair amount of thermochemical data has been accumulated on the compounds in the uranium-carbon system. The main difficulties involved appear to be the sluggishness of the reaction of these carbides and the lack of information on the true equilibrium diagram. The information assessed in this report is accurate to, say ± 5 kcal on the average. This is in fact satisfactory for quite a number of calculations of equilibria involving uranium and carbon. It is not accurate enough for more ambitious calculations such as that of the equilibrium diagram. Present assessment has also made clear the gaps that still exist. It appears that it is mainly the non-stoichiometric parts of the diagram that need extensive further studies; this would also assist in increasing the accuracy of the known data. 66 refs, 6 figs, 15 tabs

Thermochemical biorefinery based on dimethyl ether as intermediate: Technoeconomic assessment

International Nuclear Information System (INIS)

Haro, P.; Ollero, P.; Villanueva Perales, A.L.; Gómez-Barea, A.

2013-01-01

Highlights: ► A thermochemical biorefinery based on bio-DME as intermediate is studied. ► The assessed concepts (12) lead to multi-product generation (polygeneration). ► In all concepts DME is converted by carbonylation or hydrocarbonylation. ► Rates of return are similar to or higher than plants producing a single product. -- Abstract: Thermochemical biorefinery based on dimethyl ether (DME) as an intermediate is studied. DME is converted into methyl acetate, which can either be hydrogenated to ethanol or sold as a co-product. Considering this option together with a variety of technologies for syngas upgrading, 12 different process concepts are analyzed. The considered products are ethanol, methyl acetate, H 2 , DME and electricity. The assessment of each alternative includes biomass pretreatment, gasification, syngas clean-up and conditioning, DME synthesis and conversion, product separation, and heat and power integration. A plant size of 500 MW th processing poplar chips is taken as a basis. The resulting energy efficiency to products ranges from 34.9% to 50.2%. The largest internal rate of return (28.74%) corresponds to a concept which produces methyl acetate, DME and electricity (exported to grid). A sensitivity analysis with respect to total plant investment (TPI), total operation costs (TOC) and market price of products was carried out. The overall conclusion is that, despite its greater complexity, this kind of thermochemical biorefinery is more profitable than thermochemical bioprocesses oriented to a single product.

Thermochemical stability of Soviet macroporous sulfonated cation-exchangers

Energy Technology Data Exchange (ETDEWEB)

Rukhlyada, N.N.; Plotnikova, V.P.; Roginskaya, B.S.; Znamenskii, Yu.P.; Zavodovskaya, A.S.; Dobrova, E.I.

1988-10-20

The purpose of this work was to study the influence of macroporosity on the thermochemical stability of sulfonated cation-exchangers. The investigations were carried out on commercial macroporous sulfonated cation-exchangers based on styrene-divinylbenzene copolymers. Study of the thermochemical stability of macroporous sulfonated cation-exchangers in dilute hydrogen peroxide solutions showed that the type of macroporosity has virtually no influence on their stability. The determining factor in thermal stability of macroporous cation-exchangers, as of the gel type, is the degree of cross-linking of the polymer matrix. The capacity loss of macroporous cation-exchangers during oxidative thermolysis is caused by destruction of the macromolecular skeleton and elution of fragments of polar chains containing sulfo groups into the solution.

Quantitative Thermochemical Measurements in High-Pressure Gaseous Combustion

Science.gov (United States)

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.

Effects of thermo-chemical pre-treatment on anaerobic biodegradability and hydrolysis of lignocellulosic biomass

NARCIS (Netherlands)

Fernandes, T.; Klaasse Bos, G.J.; Zeeman, G.; Sanders, J.P.M.; Lier, van J.B.

2009-01-01

The effects of different thermo-chemical pre-treatment methods were determined on the biodegradability and hydrolysis rate of lignocellulosic biomass. Three plant species, hay, straw and bracken were thermo-chemically pre-treated with calcium hydroxide, ammonium carbonate and maleic acid. After

2011 Biomass Program Platform Peer Review. Thermochemical Conversion

Energy Technology Data Exchange (ETDEWEB)

Grabowski, Paul E. [Office of Energy Efficiency and Renewable Energy (EERE), Washington, DC (United States)

2012-02-01

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.

The reaction of hydrazine nitrate with nitric acid

International Nuclear Information System (INIS)

Kida, Takashi; Sugikawa, Susumu

2004-03-01

It is known that hydrazine nitrate used in nuclear fuel reprocessing plants is an unstable substance thermochemically like hydroxylamine nitrate. In order to take the basic data regarding the reaction of hydrazine nitrate with nitric acid, initiation temperatures and heats of this reaction, effect of impurity on initiation temperature and self-accelerating reaction when it holds at constant temperature for a long time were measured by the pressure vessel type reaction calorimeter etc. In this paper, the experimental data and evaluation of the safe handling of hydrazine nitrate in nuclear fuel reprocessing plants are described. (author)

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

Science.gov (United States)

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.

A 2D nickel-based energetic MOFs incorporating 3,5-diamino-1,2,4-triazole and malonic acid: Synthesis, crystal structure and thermochemical study

International Nuclear Information System (INIS)

Yang, Qi; Song, Xiaxia; Ge, Jing; Zhao, Guowei; Zhang, Wendou; Xie, Gang; Chen, Sanping; Gao, Shengli

2016-01-01

Highlights: • An energetic MOFs with dinuclear nickel unit has been synthesized and characterized. • The Arrhenius equation, derived from kinetics analysis, is ln k = 55.89 − 332.01 × 10 3 /RT. • The standard molar enthalpy of formation of the compound is determined by a thermochemical cycle. • The molar heat capacity at T = 298.15 K is determined to be 1.42 ± 0.11 J · K −1 · g −1 . - Abstract: A new energetic MOFs, {[Ni 2 (C 2 H 5 N 5 ) 2 (C 3 H 2 O 4 ) 2 (H 2 O)]·3H 2 O} n (Hdatrz (C 2 H 5 N 5 ) = 3,5-diamino-1,2,4-triazole, H 2 mal (C 3 H 4 O 4 ) = malonic acid), has been synthesized and characterized by element analysis, chemical analysis, IR spectroscopy, single-crystal X-ray diffraction and thermal analysis. X-ray diffraction analysis confirmed that the compound featured a 2D layer structure with dinuclear Ni(II) unit. Thermal analysis demonstrated that the compound after dehydration have good thermostability with decomposition temperature up to 633 K. The non-isothermal kinetics for the compound was studied by Kissinger’s and Ozawa’s methods. The Arrhenius equation of initial thermal decomposition process of compound can be expressed as ln k = 55.89 − 332.01 × 10 3 /RT. Furthermore, a reasonable thermochemical cycle was designed based on the preparation reaction of the compound, and standard molar enthalpy of dissolution of reactants and products were measured by RD496-2000 calorimeter. Finally, the standard molar enthalpy of formation of the compound was determined to be −(2766.3 ± 2.3) kJ · mol −1 in accordance with Hess’s law. In addition, the specific heat capacity of the compound at T = 298.15 K was determined to be 1.42 ± 0.11 J · K −1 · g −1 by RD496-2000 calorimeter.

Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

Energy Technology Data Exchange (ETDEWEB)

Hafsteinsdottir, Erla G., E-mail: erla.hafsteinsdottir@gmail.com [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); White, Duanne A., E-mail: duanne.white@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Gore, Damian B., E-mail: damian.gore@mq.edu.au [Department of Environment and Geography, Macquarie University, NSW 2109 (Australia); Stark, Scott C., E-mail: scott.stark@aad.gov.au [Environmental Protection and Change, Australian Antarctic Division, Department of Sustainability, Environment, Water, Population and Communities, Tasmania 7050 (Australia)

2011-12-15

Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H{sub 2}PO{sub 4}){sub 2}] or sodium phosphate [Na{sub 3}PO{sub 4}]) reacts with lead (PbSO{sub 4} or PbCl{sub 2}) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 deg. C to -20 deg. C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO{sub 4} and Na{sub 3}PO{sub 4} were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate. - Highlights: > Formation of lead phosphate products in cold environments is identified. > Potential change in formation during freeze-thaw cycling is assessed. > Lead phosphate reaction efficiency varies according to phosphate and lead source. > Pyromorphite formation is stable during 240 freeze-thaw cycles. - Pyromorphite, formed from Pb phosphate fixation, is stable during multiple freeze-thaw cycles but the efficiency of the fixation depends on the phosphate source and the type of Pb mineral.

R and D thermochemical I-S process at JAERI

International Nuclear Information System (INIS)

Onuki, K.; Kubo, S.; Nakajima, H.; Higashi, S.; Kasahara, S.; Ishiyama, S.; Okuda, H.

2004-01-01

The Japan Atomic Energy Research Institute (JAERI) has conducted a study on the thermochemical water-splitting process of the iodine-sulfur family (IS process). In the IS process, water will react with iodine and sulfur dioxide to produce hydrogen iodide and sulfuric acid, which are then decomposed thermally to produce hydrogen and oxygen. High temperature nuclear heat, mainly supplied by a High Temperature Gas-cooled Reactor (HTGR), is used to drive the endothermic decomposition of sulfuric acid. JAERI has demonstrated the feasibility of the water-splitting hydrogen production process by carrying out laboratory-scale experiments in which combined operation of fundamental reactions and separations using the IS process was performed continuously. At present, the hydrogen production test is continuing, using a scaled-up glass apparatus. Corrosion-resistant materials for constructing a large-scale plant and process improvements by introducing advanced separation techniques, such as membrane separation, are under study. Future R and D items are discussed based on the present activities. (author)

Thermochemical hydrogen generation of indium oxide thin films

Directory of Open Access Journals (Sweden)

Taekyung Lim

2017-03-01

Full Text Available Development of alternative energy resources is an urgent requirement to alleviate current energy constraints. As such, hydrogen gas is gaining attention as a future alternative energy source to address existing issues related to limited energy resources and air pollution. In this study, hydrogen generation by a thermochemical water-splitting process using two types of In2O3 thin films was investigated. The two In2O3 thin films prepared by chemical vapor deposition (CVD and sputtering deposition systems contained different numbers of oxygen vacancies, which were directly related to hydrogen generation. The as-grown In2O3 thin film prepared by CVD generated a large amount of hydrogen because of its abundant oxygen vacancies, while that prepared by sputtering had few oxygen vacancies, resulting in low hydrogen generation. Increasing the temperature of the In2O3 thin film in the reaction chamber caused an increase in hydrogen generation. The oxygen-vacancy-rich In2O3 thin film is expected to provide a highly effective production of hydrogen as a sustainable and efficient energy source.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

Energy Technology Data Exchange (ETDEWEB)

Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver, E-mail: jasmina@physics.ucf.edu [Planetary Sciences Group, Department of Physics, University of Central Florida, Orlando, FL 32816-2385 (United States)

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 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.

TEA: A CODE CALCULATING THERMOCHEMICAL EQUILIBRIUM ABUNDANCES

International Nuclear Information System (INIS)

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

2016-01-01

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 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.

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

Science.gov (United States)

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.

SUNgas: Thermochemical Approaches to Solar Fuels

Science.gov (United States)

Davidson, Jane

2013-04-01

Solar energy offers an intelligent solution to reduce anthropogenic emissions of greenhouse gases and to meet an expanding global demand for energy. A transformative change from fossil to solar energy requires collection, storage, and transport of the earth's most abundant but diffuse and intermittent source of energy. One intriguing approach for harvest and storage of solar energy is production of clean fuels via high temperature thermochemical processes. Concentrated solar energy is the heat source and biomass or water and carbon dioxide are the feedstocks. Two routes to produce fuels using concentrated solar energy and a renewable feed stock will be discussed: gasification of biomass or other carbonaceous materials and metal oxide cycles to produce synthesis gas. The first and most near term route to solar fuels is to gasify biomass. With conventional gasification, air or oxygen is supplied at fuel-rich levels to combust some of the feedstock and in this manner generate the energy required for conversion to H2 and CO. The partial-combustion consumes up to 40% of the energetic value of the feedstock. With air combustion, the product gas is diluted by high levels of CO2 and N2. Using oxygen reduces the product dilution, but at the expense of adding an oxygen plant. Supplying the required heat with concentrated solar radiation eliminates the need for partial combustion of the biomass feedstock. As a result, the product gas has an energetic value greater than that of the feedstock and it is not contaminated by the byproducts of combustion. The second promising route to solar fuels splits water and carbon dioxide. Two-step metal-oxide redox cycles hold out great potential because they the temperature required to achieve a reasonable degree of dissociation is lower than direct thermal dissociation and O2 and the fuel are produced in separate steps. The 1^st step is the endothermic thermal dissociation of the metal oxide to the metal or lower-valence metal oxide. The 2

Investigation of thermodynamic performances for two solar-biomass hybrid combined cycle power generation systems

International Nuclear Information System (INIS)

Liu, Qibin; Bai, Zhang; Wang, Xiaohe; Lei, Jing; Jin, Hongguang

2016-01-01

Highlights: • Two solar-biomass hybrid combined cycle power generation systems are proposed. • The characters of the two proposed systems are compared. • The on-design and off-design properties of the system are numerically investigated. • The favorable performances of thermochemical hybrid routine are validated. - Abstract: Two solar-biomass hybrid combined cycle power generation systems are proposed in this work. The first system employs the thermochemical hybrid routine, in which the biomass gasification is driven by the concentrated solar energy, and the gasified syngas as a solar fuel is utilized in a combined cycle for generating power. The second system adopts the thermal integration concept, and the solar energy is directly used to heat the compressed air in the topping Brayton cycle. The thermodynamic performances of the developed systems are investigated under the on-design and off-design conditions. The advantages of the hybrid utilization technical mode are demonstrated. The solar energy can be converted and stored into the chemical fuel by the solar-biomass gasification, with the net solar-to-fuel efficiency of 61.23% and the net solar share of 19.01% under the specific gasification temperature of 1150 K. Meanwhile, the proposed system with the solar thermochemical routine shows more favorable behaviors, the annual system overall energy efficiency and the solar-to-electric efficiency reach to 29.36% and 18.49%, while the with thermal integration concept of 28.03% and 15.13%, respectively. The comparison work introduces a promising approach for the efficient utilization of the abundant solar and biomass resources in the western China, and realizes the mitigation of CO_2 emission.

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

Directory of Open Access Journals (Sweden)

Sophia Haussener

2012-01-01

Full Text Available 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.

Effective reaction rates in diffusion-limited phosphorylation-dephosphorylation cycles

Science.gov (United States)

Szymańska, Paulina; Kochańczyk, Marek; Miekisz, Jacek; Lipniacki, Tomasz

2015-02-01

We investigate the kinetics of the ubiquitous phosphorylation-dephosphorylation cycle on biological membranes by means of kinetic Monte Carlo simulations on the triangular lattice. We establish the dependence of effective macroscopic reaction rate coefficients as well as the steady-state phosphorylated substrate fraction on the diffusion coefficient and concentrations of opposing enzymes: kinases and phosphatases. In the limits of zero and infinite diffusion, the numerical results agree with analytical predictions; these two limits give the lower and the upper bound for the macroscopic rate coefficients, respectively. In the zero-diffusion limit, which is important in the analysis of dense systems, phosphorylation and dephosphorylation reactions can convert only these substrates which remain in contact with opposing enzymes. In the most studied regime of nonzero but small diffusion, a contribution linearly proportional to the diffusion coefficient appears in the reaction rate. In this regime, the presence of opposing enzymes creates inhomogeneities in the (de)phosphorylated substrate distributions: The spatial correlation function shows that enzymes are surrounded by clouds of converted substrates. This effect becomes important at low enzyme concentrations, substantially lowering effective reaction rates. Effective reaction rates decrease with decreasing diffusion and this dependence is more pronounced for the less-abundant enzyme. Consequently, the steady-state fraction of phosphorylated substrates can increase or decrease with diffusion, depending on relative concentrations of both enzymes. Additionally, steady states are controlled by molecular crowders which, mostly by lowering the effective diffusion of reactants, favor the more abundant enzyme.

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

Science.gov (United States)

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.

Prototype thermochemical heat storage with open reactor system

NARCIS (Netherlands)

Zondag, H.A.; Kikkert, B.; Smeding, S.F.; Boer, de R.; Bakker, M.

2013-01-01

Thermochemical (TC) heat storage is an interesting technology for future seasonal storage of solar heat in the built environment. This technology enables high thermal energy storage densities and low energy storage losses. A small-scale laboratory prototype TC storage system has been realized at

A systematic multi-step screening of numerous salt hydrates for low temperature thermochemical energy storage

International Nuclear Information System (INIS)

N’Tsoukpoe, Kokouvi Edem; Schmidt, Thomas; Rammelberg, Holger Urs; Watts, Beatriz Amanda; Ruck, Wolfgang K.L.

2014-01-01

Highlights: • We report an evaluation of the potential of salt hydrates for thermochemical storage. • Both theoretical calculations and experimental measurements using TGA/DSC are used. • Salt hydrates offer very low potential for thermochemical heat storage. • The efficiency of classical processes using salt hydrates is very low: typically 25%. • New processes are needed for the use of salt hydrates in thermochemical heat storage. - Abstract: In this paper, the potential energy storage density and the storage efficiency of salt hydrates as thermochemical storage materials for the storage of heat generated by a micro-combined heat and power (micro-CHP) have been assessed. Because salt hydrates used in various thermochemical heat storage processes fail to meet the expectations, a systematic evaluation of the suitability of 125 salt hydrates has been performed in a three-step approach. In the first step general issues such as toxicity and risk of explosion have been considered. In the second and third steps, the authors implement a combined approach consisting of theoretical calculations and experimental measurements using Thermogravimetric Analysis (TGA). Thus, application-oriented comparison criteria, among which the net energy storage density of the material and the thermal efficiency, have been used to evaluate the potential of 45 preselected salt hydrates for a low temperature thermochemical heat storage application. For an application that requires a discharging temperature above 60 °C, SrBr 2 ·6H 2 O and LaCl 3 ·7H 2 O appear to be the most promising, only from thermodynamic point of view. However, the maximum net energy storage density including the water in the water storage tank that they offer (respectively 133 kW h m −3 and 89 kW h m −3 ) for a classical thermochemical heat storage process are not attractive for the intended application. Furthermore, the thermal efficiency that would result from the storage process based on salt hydrates

The NREL Biochemical and Thermochemical Ethanol Conversion Processes: Financial and Environmental Analysis Comparison

Directory of Open Access Journals (Sweden)

Jesse Sky Daystar

2015-07-01

Full Text Available The financial and environmental performance of the National Renewable Energy Lab’s (NREL thermochemical and biochemical biofuel conversion processes are examined herein with pine, eucalyptus, unmanaged hardwood, switchgrass, and sweet sorghum. The environmental impacts of the process scenarios were determined by quantifying greenhouse gas (GHG emissions and TRACI impacts. Integrated financial and environmental performance metrics were introduced and used to examine the biofuel production scenarios. The thermochemical and biochemical conversion processes produced the highest financial performance and lowest environmental impacts when paired with pine and sweet sorghum, respectively. The high ash content of switchgrass and high lignin content of loblolly pine lowered conversion yields, resulting in the highest environmental impacts and lowest financial performance for the thermochemical and biochemical conversion processes, respectively. Biofuel produced using the thermochemical conversion process resulted in lower TRACI single score impacts and somewhat lower GHG emissions per megajoule (MJ of fuel than using the biochemical conversion pathway. The cost of carbon mitigation resulting from biofuel production and corresponding government subsidies was determined to be higher than the expected market carbon price. In some scenarios, the cost of carbon mitigation was several times higher than the market carbon price, indicating that there may be other more cost-effective methods of reducing carbon emissions.

Solar High Temperature Water-Splitting Cycle with Quantum Boost

Energy Technology Data Exchange (ETDEWEB)

Taylor, Robin [SAIC; Davenport, Roger [SAIC; Talbot, Jan [UCSD; Herz, Richard [UCSD; Genders, David [Electrosynthesis Co.; Symons, Peter [Electrosynthesis Co.; Brown, Lloyd [TChemE

2014-04-25

A sulfur family chemical cycle having ammonia as the working fluid and reagent was developed as a cost-effective and efficient hydrogen production technology based on a solar thermochemical water-splitting cycle. The sulfur ammonia (SA) cycle is a renewable and sustainable process that is unique in that it is an all-fluid cycle (i.e., with no solids handling). It uses a moderate temperature solar plant with the solar receiver operating at 800°C. All electricity needed is generated internally from recovered heat. The plant would operate continuously with low cost storage and it is a good potential solar thermochemical hydrogen production cycle for reaching the DOE cost goals. Two approaches were considered for the hydrogen production step of the SA cycle: (1) photocatalytic, and (2) electrolytic oxidation of ammonium sulfite to ammonium sulfate in aqueous solutions. Also, two sub-cycles were evaluated for the oxygen evolution side of the SA cycle: (1) zinc sulfate/zinc oxide, and (2) potassium sulfate/potassium pyrosulfate. The laboratory testing and optimization of all the process steps for each version of the SA cycle were proven in the laboratory or have been fully demonstrated by others, but further optimization is still possible and needed. The solar configuration evolved to a 50 MW(thermal) central receiver system with a North heliostat field, a cavity receiver, and NaCl molten salt storage to allow continuous operation. The H2A economic model was used to optimize and trade-off SA cycle configurations. Parametric studies of chemical plant performance have indicated process efficiencies of ~20%. Although the current process efficiency is technically acceptable, an increased efficiency is needed if the DOE cost targets are to be reached. There are two interrelated areas in which there is the potential for significant efficiency improvements: electrolysis cell voltage and excessive water vaporization. Methods to significantly reduce water evaporation are

The calculation of specific heats for some important solid components in hydrogen production process based on CuCl cycle

Directory of Open Access Journals (Sweden)

Avsec Jurij

2014-01-01

Full Text Available Hydrogen is one of the most promising energy sources of the future enabling direct production of power and heat in fuel cells, hydrogen engines or furnaces with hydrogen burners. One of the last remainder problems in hydrogen technology is how to produce a sufficient amount of cheap hydrogen. One of the best options is large scale thermochemical production of hydrogen in combination with nuclear power plant. copper-chlorine (CuCl cycle is the most promissible thermochemical cycle to produce cheap hydrogen.This paper focuses on a CuCl cycle, and the describes the models how to calculate thermodynamic properties. Unfortunately, for many components in CuCl cycle the thermochemical functions of state have never been measured. This is the reason that we have tried to calculate some very important thermophysical properties. This paper discusses the mathematical model for computing the thermodynamic properties for pure substances and their mixtures such as CuCl, HCl, Cu2OCl2 important in CuCl hydrogen production in their fluid and solid phase with an aid of statistical thermodynamics. For the solid phase, we have developed the mathematical model for the calculation of thermodynamic properties for polyatomic crystals. In this way, we have used Debye functions and Einstein function for acoustical modes and optical modes of vibrations to take into account vibration of atoms. The influence of intermolecular energy we have solved on the basis of Murnaghan equation of state and statistical thermodynamics.

Thermochemical recycling of mixture of scrap tyres and waste lubricating oil into high caloric value products

International Nuclear Information System (INIS)

Abdul-Raouf, Manar E.; Maysour, Nermine E.; Abdul-Azim, Abdul-Azim A.; Amin, Mahasen S.

2010-01-01

Scrap tyres and used lubricating oils represent together growing environmental problem because they are not biodegradable and their components cannot readily be recovered. In the present investigation, the thermochemical recycling of mixture of old tyres with waste lubricating oil by pyrolysis and the value of the products obtained have been studied. First, thermobalance experiments were carried out, studying the influence of the following variables: temperature, type of catalyst and catalyst concentration on the pyrolysis reaction of a mixture of 1/1 wt./wt. oil/tyre ratio. These thermobalance results were thoroughly investigated to study the effect of the main process variables on yields of derived products: oils, gases and solid residue.

Application of lithium orthosilicate for high-temperature thermochemical energy storage

International Nuclear Information System (INIS)

Takasu, Hiroki; Ryu, Junichi; Kato, Yukitaka

2017-01-01

Highlights: • Li_4SiO_4/CO_2 system is proposed for use in chemical heat pump systems at 650 and 700 °C. • Li_4SiO_4/CO_2 system showed an enough cyclic reaction durability for 5 cycles. • The energy storage density of Li_4SiO_4 was estimated to be 750 kJ L"−"1 and 780 kJ kg"−"1. • It was demonstrated that Li_4SiO_4 could be used as a thermal heat storage material. - Abstract: A lithium orthosilicate/carbon dioxide (Li_4SiO_4/CO_2) reaction system is proposed for use in thermochemical energy storage (TcES) and chemical heat pump (CHP) systems at around 700 °C. Carbonation of Li_4SiO_4 exothermically produces lithium carbonate (Li_2CO_3) and lithium metasilicate (Li_2SiO_3). Decarbonation of these products is used for heat storage, and carbonation is used for heat output in a TcES system. A Li_4SiO_4 sample around 20 μm in diameter was prepared from Li_2CO_3 and SiO_2 using a solid-state reaction method. To determine the reactivity of the sample, Li_4SiO_4 carbonation and decarbonation experiments were conducted under CO_2 at several pressures in a closed reactor using thermogravimetric analysis. The Li_4SiO_4 sample’s carbonation and decarbonation performance was sufficient for use as a TcES material at around 700 °C. In addition, both reaction temperatures of Li_4SiO_4 varied with the CO_2 pressure. The durability under repeated Li_4SiO_4 carbonation and decarbonation was tested using temperature swing and pressure swing methods. Both methods showed that the Li_4SiO_4 sample has sufficient durability. These results indicate that the temperature for heat storage and heat output by carbonation and decarbonation, respectively, could be controlled by controlling the CO_2 pressure. Li_4SiO_4/CO_2 can be used not only for TcES but also in CHPs. The volumetric and gravimetric thermal energy densities of Li_4SiO_4 for TcES were found to be 750 kJ L"−"1 and 780 kJ kg"−"1, where the porosity of Li_4SiO_4 was assumed to be 59%. When the reaction system

Thermo-chemical Ice Penetrator for Icy Moons

Science.gov (United States)

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

2016-12-01

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

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

Science.gov (United States)

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

2016-05-01

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

Thermochemical cycles for the production of hydrogen

Science.gov (United States)

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.

Thermochemical study of MoS2 oxidation

International Nuclear Information System (INIS)

Filimonov, D.S.; Topor, N.D.; Kesler, Ya.A.

1990-01-01

Thermochemical studies of oxidation processes of metallic molybdenum, sulfur, molybdenum disulfide under different conditions in microcalorimeter are conducted. Values of thermal effects which are used to calculate standard formation enthalpy of MoS 2 and which correlate well are obtained. Δ f H 0 (MoS 2 ,298.15 K) recommended value constitutes (-223.0±16.7) kJ/mol

Global warming potential of the sulfur-iodine process using life cycle assessment methodology

International Nuclear Information System (INIS)

Lattin, William C.; Utgikar, Vivek P.

2009-01-01

A life cycle assessment (LCA) of one proposed method of hydrogen production - thermochemical water-splitting using the sulfur-iodine cycle couple with a very high-temperature nuclear reactor - is presented in this paper. Thermochemical water-splitting theoretically offers a higher overall efficiency than high-temperature electrolysis of water because heat from the nuclear reactor is provided directly to the hydrogen generation process, instead of using the intermediate step of generating electricity. The primary heat source for the S-I cycle is an advanced nuclear reactor operating at temperatures corresponding to those required by the sulfur-iodine process. This LCA examines the environmental impact of the combined advanced nuclear and hydrogen generation plants and focuses on quantifying the emissions of carbon dioxide per kilogram of hydrogen produced. The results are presented in terms of global warming potential (GWP). The GWP of the system is 2500 g carbon dioxide-equivalent (CO 2 -eq) per kilogram of hydrogen produced. The GWP of this process is approximately one-sixth of that for hydrogen production by steam reforming of natural gas, and is comparable to producing hydrogen from wind- or hydro-electric conventional electrolysis. (author)

Achievement report on research and development in the Sunshine Project in fiscal 1977. Research and development of water decomposition using mixture cycles composed by thermo-chemistry, photo-chemistry and electrochemistry; 1977 nendo netsukagaku, hikari kagaku, denki kagaku konsei cycle ni yoru suibunkai no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1978-03-01

Discussions are being made on manufacture of hydrogen and oxygen from water decomposition using mixture cycles composed by thermo-chemistry, photo-chemistry and electrochemistry using ferrous sulfate and iodine. Photo-chemical reaction produces Fe(OH)SO{sub 4} and HI, but due to difficulty of isolating Fe(OH)SO{sub 4}, photo-chemical reaction that can obtain the compound as Fe{sub 2}(SO{sub 4}){sub 3} was introduced. A method was introduced that can perform HI isolation simultaneously while performing reaction to reduce Fe{sup 3+} and turn it into Fe{sup 2+} (generating oxygen) by means of electrolysing the liquid after the former reaction. The electrolytic process decomposes HI into hydrogen and iodine (discussions on thermo-chemical decomposition is also continued). Since the photo-chemical reaction can cause reverse reaction, discussions were given on the reaction process in order to suppress the reverse reaction and enhance the conversion efficiency. This paper describes the achievements during fiscal 1977. A quantification method was elucidated on individual iodine components so that it can be used for computerized control (measurement of absorbance of I{sub 3}{sup -}) . An electrolytic tank was discussed that decomposes and isolates photo-chemical reaction products before the reverse reaction occurs. Heat diffusion method was also discussed that isolates hydrogen from HI decomposition products. (NEDO)

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

Science.gov (United States)

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.

The NAGRA/PSI thermochemical database: new developments

International Nuclear Information System (INIS)

Hummel, W.; Berner, U.; Thoenen, T.; Pearson, F.J.Jr.

2000-01-01

The development of a high quality thermochemical database for performance assessment is a scientifically fascinating and demanding task, and is not simply collecting and recording numbers. The final product can by visualised as a complex building with different storeys representing different levels of complexity. The present status report illustrates the various building blocks which we believe are integral to such a database structure. (authors)

The NAGRA/PSI thermochemical database: new developments

Energy Technology Data Exchange (ETDEWEB)

Hummel, W.; Berner, U.; Thoenen, T. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Pearson, F.J.Jr. [Ground-Water Geochemistry, New Bern, NC (United States)

2000-07-01

The development of a high quality thermochemical database for performance assessment is a scientifically fascinating and demanding task, and is not simply collecting and recording numbers. The final product can by visualised as a complex building with different storeys representing different levels of complexity. The present status report illustrates the various building blocks which we believe are integral to such a database structure. (authors)

Thermochemical structure of the Earth's mantle and continental crust

DEFF Research Database (Denmark)

Guerri, Mattia

A detailed knowledge of the Earth's thermal structure and chemical composition is fundamental in order to understand the processes driving the planet ormation and evolution. The inaccessibility of most of the Earth's interior makes the determination of its thermo-chemical conditions a challenging...

REITP3-Hazard evaluation program for heat release based on thermochemical calculation

Energy Technology Data Exchange (ETDEWEB)

Akutsu, Yoshiaki.; Tamura, Masamitsu. [The University of Tokyo, Tokyo (Japan). School of Engineering; Kawakatsu, Yuichi. [Oji Paper Corp., Tokyo (Japan); Wada, Yuji. [National Institute for Resources and Environment, Tsukuba (Japan); Yoshida, Tadao. [Hosei University, Tokyo (Japan). College of Engineering

1999-06-30

REITP3-A hazard evaluation program for heat release besed on thermochemical calculation has been developed by modifying REITP2 (Revised Estimation of Incompatibility from Thermochemical Properties{sup 2)}. The main modifications are as follows. (1) Reactants are retrieved from the database by chemical formula. (2) As products are listed in an external file, the addition of products and change in order of production can be easily conducted. (3) Part of the program has been changed by considering its use on a personal computer or workstation. These modifications will promote the usefulness of the program for energy hazard evaluation. (author)

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

Science.gov (United States)

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 (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

Thermochemical recycling of mixture of scrap tyres and waste lubricating oil into high caloric value products

Energy Technology Data Exchange (ETDEWEB)

Abdul-Raouf, Manar E.; Maysour, Nermine E.; Abdul-Azim, Abdul-Azim A. [Egyptian Petroleum Research Institute, Nasr City, Cairo (Egypt); Amin, Mahasen S. [Faculty of Science, Benha University, Benha (Egypt)

2010-06-15

Scrap tyres and used lubricating oils represent together growing environmental problem because they are not biodegradable and their components cannot readily be recovered. In the present investigation, the thermochemical recycling of mixture of old tyres with waste lubricating oil by pyrolysis and the value of the products obtained have been studied. First, thermobalance experiments were carried out, studying the influence of the following variables: temperature, type of catalyst and catalyst concentration on the pyrolysis reaction of a mixture of 1/1 wt./wt. oil/tyre ratio. These thermobalance results were thoroughly investigated to study the effect of the main process variables on yields of derived products: oils, gases and solid residue. (author)

Analysis of hot spots in boilers of organic Rankine cycle units during transient operation

DEFF Research Database (Denmark)

Benato, A.; Kærn, Martin Ryhl; Pierobon, Leonardo

2015-01-01

This paper is devoted to the investigation of critical dynamic events causing thermochemical decompositionof the working fluid in organic Rankine cycle power systems. The case study is the plant of an oiland gas platform where one of the three gas turbines is combined with an organic Rankine cycle...... and fluid decomposition. It is demonstrated thatthe use of a spray attemperator can mitigate the problems of local overheating of the organic compound.As a practical consequence, this paper provides guidelines for safe and reliable operation of organicRankine cycle power modules on offshore installations....

Probabilistic thermo-chemical analysis of a pultruded composite rod

DEFF Research Database (Denmark)

Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

2012-01-01

In the present study the deterministic thermo-chemical pultrusion simulation of a composite rod taken from the literature [7] is used as a validation case. The predicted centerline temperature and cure degree profiles of the rod match well with those in the literature [7]. Following the validation...

THE RESPIRATORY SUBSTRATE RHODOQUINOL INDUCES Q-CYCLE BYPASS REACTIONS IN THE YEAST CYTOCHROME bc1 COMPLEX - MECHANISTIC AND PHYSIOLOGICAL IMPLICATIONS

International Nuclear Information System (INIS)

Cape, Jonathan L.; Strahan, Jeff R.; Lenaeus, Michael J.; Yuknis, Brook A.; Le, Trieu T.; Shepherd, Jennifer; Bowman, Michael K.; Kramer, David M.

2005-01-01

The mitochondrial cytochrome bc1 complex catalyzes the transfer of electrons from ubiquinol to cyt c, while generating a proton motive force for ATP synthesis, via the ''Qcycle'' mechanism. Under certain conditions, electron flow through the Q-cycle is blocked at the level of a reactive intermediate in the quinol oxidase site of the enzyme, resulting in ''bypass reactions'', some of which lead to superoxide production. Using analogs of the respiratory substrates, ubiquinol-3 and rhodoquinol-3, we show that the relative rates of Q-cycle bypass reactions in the Saccharomyces cerevisiae cyt bc1 complex are highly dependent, by a factor of up to one hundred-fold, on the properties of the substrate quinol. Our results suggest that the rate of Q-cycle bypass reactions is dependent on the steady state concentration of reactive intermediates produced at the quinol oxidase site of the enzyme. We conclude that normal operation of the Q-cycle requires a fairly narrow window of redox potentials, with respect to the quinol substrate, to allow normal turnover of the complex while preventing potentially damaging bypass reactions

Thermochemical conversion of microalgal biomass into biofuels: a review.

Science.gov (United States)

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.

Trans-methylation reactions in plants: focus on the activated methyl cycle.

Science.gov (United States)

Rahikainen, Moona; Alegre, Sara; Trotta, Andrea; Pascual, Jesús; Kangasjärvi, Saijaliisa

2018-02-01

Trans-methylation reactions are vital in basic metabolism, epigenetic regulation, RNA metabolism, and posttranslational control of protein function and therefore fundamental in determining the physiological processes in all living organisms. The plant kingdom is additionally characterized by the production of secondary metabolites that undergo specific hydroxylation, oxidation and methylation reactions to obtain a wide array of different chemical structures. Increasing research efforts have started to reveal the enzymatic pathways underlying the biosynthesis of complex metabolites in plants. Further engineering of these enzymatic machineries offers significant possibilities in the development of bio-based technologies, but necessitates deep understanding of their potential metabolic and regulatory interactions. Trans-methylation reactions are tightly coupled with the so-called activated methyl cycle (AMC), an essential metabolic circuit that maintains the trans-methylation capacity in all living cells. Tight regulation of the AMC is crucial in ensuring accurate trans-methylation reactions in different subcellular compartments, cell types, developmental stages and environmental conditions. This review addresses the organization and posttranslational regulation of the AMC and elaborates its critical role in determining metabolic regulation through modulation of methyl utilization in stress-exposed plants. © 2017 Scandinavian Plant Physiology Society.

Combustion kinetics and reaction pathways

Energy Technology Data Exchange (ETDEWEB)

Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

1993-12-01

This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

Application of Thermochemical Modeling to Assessment/Evaluation of Nuclear Fuel Behavior

Energy Technology Data Exchange (ETDEWEB)

Besmann, Theodore M [University of South Carolina, Columbia; McMurray, Jake W [ORNL; Simunovic, Srdjan [ORNL

2016-01-01

The combination of new fuel compositions and higher burn-ups envisioned for the future means that representing fuel properties will be much more important, and yet more complex. Behavior within the oxide fuel rods will be difficult to model owing to the high temperatures, and the large number of elements generated and their significant concentrations that are a result of fuels taken to high burn-up. This unprecedented complexity offers an enormous challenge to the thermochemical understanding of these systems and opportunities to advance solid solution models to describe these materials. This paper attempts to model and simulate that behavior using an oxide fuels thermochemical description to compute the equilibrium phase state and oxygen potential of LWR fuel under irradiation.

Consequences of poly(vinyl chloride) presence on the thermochemical process of lignocellulosic biomass in CO₂ by thermogravimetric analysis.

Science.gov (United States)

He, Yao; Ma, Xiaoqian; Zeng, Guangbo

2015-02-01

The thermochemical processes of lignocellulosic biomass and its mixtures with poly(vinyl chloride) (PVC) fractions were investigated by thermogravimetric analysis in CO2 atmosphere. Superposition property was assumed to examine whether and/or to what extent interactions occurred during the mixture decomposition. Results showed that interactions existed, of which the intensities changed with reaction stage, heating rate and PVC quantity, and they actively behaved toward the decomposition in most cases. With PVC presence, lignocellulosic biomass turned from three-stage to four-stage decomposition process where the reactions occurred at lower temperatures with heightened intensity, especially in the first stage. The measured activation energies calculated by Ozawa-Flynn-Wall and Vyazovkin methods were of minor difference <5 kJ/mol, and comparing them between materials in each stage confirmed the results of interaction impact. This work provides a theoretical basis bringing about the possibilities of recycling CO2 into a reaction medium of thermo-treatment of lignocellulosic material with PVC contaminants. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermochemical methods for the treatment of oil contaminated sand; Metodo termoquimico para tratamento de areia contaminada por oleo

Energy Technology Data Exchange (ETDEWEB)

Pimenta, Rosana C.G.M. [Fundacao Jose Bonifacio, Rio de Janeiro, RJ (Brazil); Khalil, Carlos N. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil)

2003-07-01

The Nitrogen Generating System (SGN in Portuguese) is a thermochemical method first developed for cleaning and removal of paraffin deposits in production and export pipelines. SGN is based on a redox chemical reaction between two salts which is catalyzed in acidic pH. The reaction is strongly exothermic and its products are nitrogen, sodium chloride, water and heat. All reaction products are harmless to the environment. In January 2000 there was a major oil spill in Guanabara Bay, Rio de Janeiro, which contaminated 2400 tons of sand. This work, developed at PETROBRAS Research Center (CENPES), was based on SGN technology which has been adapted for cleaning contaminated sand and recovering of spilled oil. By combining simultaneous effects of the SGN treatment such as heating, turbulence and floatation, one can remove, within 98% of efficiency, spilling oil from contaminated sand and removed oil can be securely returned to refining process. SGN technology has proved to be efficient, fast, low cost and ecologically correct method for cleaning contaminated sand and can be applied in loco right after a contamination event. (author)

Ceria-based electrospun fibers for renewable fuel production via two-step thermal redox cycles for carbon dioxide splitting.

Science.gov (United States)

Gibbons, William T; Venstrom, Luke J; De Smith, Robert M; Davidson, Jane H; Jackson, Gregory S

2014-07-21

Zirconium-doped ceria (Ce(1-x)Zr(x)O2) was synthesized through a controlled electrospinning process as a promising approach to cost-effective, sinter-resistant material structures for high-temperature, solar-driven thermochemical redox cycles. To approximate a two-step redox cycle for solar fuel production, fibrous Ce(1-x)Zr(x)O2 with relatively low levels of Zr-doping (0 rates of O2 release during reduction and CO production during reoxidation and by assessing post-cycling fiber crystallite sizes and surface areas. Sintering increases with reduction temperature but occurs primarily along the fiber axes. Even after 108 redox cycles with reduction at 1400 °C and oxidation with CO2 at 800 °C, the fibers maintain their structure with surface areas of ∼0.3 m(2) g(-1), higher than those observed in the literature for other ceria-based structures operating at similarly high temperature conditions. Total CO production and peak production rate stabilize above 3.0 mL g(-1) and 13.0 mL min(-1) g(-1), respectively. The results show the potential for electrospun oxides as sinter-resistant material structures with adequate surface area to support rapid CO2 splitting in solar thermochemical redox cycles.

Thermochemical properties of the alkali hydroxides: A review

International Nuclear Information System (INIS)

Konings, R.J.M.; Cordfunke, E.H.P.

1989-01-01

The formation of volatile alkali hydroxides as a result of high-temperature steam corrosion plays an important role in nuclear technology. For the modeling of the volatilization processes, reliable thermodynamic data are required. In the present paper recent physico-chemical experiments by the authors will be discussed and the thermochemical properties of the alkali hydroxide series will be evaluated. (orig.)

Lattice potential energies and thermochemical properties of triethylammonium halides (Et3NHX) (X = Cl, Br, and I)

International Nuclear Information System (INIS)

Liu Yupu; Tan Zhicheng; Di Youying; Xing Yiting; Zhang Peng

2012-01-01

Highlights: ► The crystal structures of (Et 3 NHX) (X = Cl, Br, and I) were determined. ► Lattice potential energies and ionic radius of the common cation were obtained. ► Molar enthalpies of dissolution at infinite dilution were derived. ► Relative partial molar enthalpies were derived. ► Hydration enthalpy of Et 3 NH + was calculated. - Abstract: A series of triethylammonium halides (Et 3 NHCl, Et 3 NHBr, and Et 3 NHI) was synthesized. The crystal structures of the three compounds were characterized by X-ray crystallography. The lattice potential energies and ionic radius of the common cation of the three compounds were obtained from crystallographic data. Molar enthalpies of dissolution of the compounds at various values of molality were measured in the double-distilled water at T = 298.150 K by means of an isoperibol solution-reaction calorimeter. According to Pitzer’s theory, the values of molar enthalpies of dissolution at infinite dilution and Pitzer’s parameters of the compounds were obtained. The values of apparent relative molar enthalpies, relative partial molar enthalpies of the solvent and the compounds at different molalities were derived from the experimental values of molar enthalpies of dissolution of the compounds. Finally, hydration enthalpy of the common cation Et 3 NH + was calculated to be ΔH + = −(150.386 ± 4.071) kJ · mol −1 by designing a thermochemical cycle.

Development of hydraulic analysis code for optimizing thermo-chemical is process reactors

International Nuclear Information System (INIS)

Terada, Atsuhiko; Hino, Ryutaro; Hirayama, Toshio; Nakajima, Norihiro; Sugiyama, Hitoshi

2007-01-01

The Japan Atomic Energy Agency has been conducting study on thermochemical IS process for water splitting hydrogen production. Based on the test results and know-how obtained through the bench-scale test, a pilot test plant, which has a hydrogen production performance of 30 Nm 3 /h, is being designed conceptually as the next step of the IS process development. In design of the IS pilot plant, it is important to make chemical reactors compact with high performance from the viewpoint of plant cost reduction. A new hydraulic analytical code has been developed for optimizing mixing performance of multi-phase flow involving chemical reactions especially in the Bunsen reactor. Complex flow pattern with gas-liquid chemical interaction involving flow instability will be characterized in the Bunsen reactor. Preliminary analytical results obtained with above mentioned code, especially flow patterns induced by swirling flow agreed well with that measured by water experiments, which showed vortex breakdown pattern in a simplified Bunsen reactor. (author)

Solar thermochemical processing system and method

Science.gov (United States)

Wegeng, Robert S.; Humble, Paul H.; Krishnan, Shankar; Leith, Steven D.; Palo, Daniel R.; Dagle, Robert A.

2018-04-24

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.

Fusion as a source of synthetic fuels

International Nuclear Information System (INIS)

Powell, J.R.; Fillo, J.A.; Steinberg, M.

1981-01-01

In the near-term, coal derived synthetic fuels will be used; but in the long-term, resource depletion and environmental effects will mandate synthetic fuels from inexhaustible sources - fission, fusion, and solar. Of the three sources, fusion appears uniquely suited for the efficient production of hydrogen-based fuels, due to its ability to directly generate very high process temperatures (up to approx. 2000 0 C) for water splitting reactions. Fusion-based water splitting reactions include high temperature electrolysis (HTE) of steam, thermochemical cycles, hybrid electrochemical/thermochemical, and direct thermal decomposition. HTE appears to be the simplest and most efficient process with efficiencies of 50 to 70% (fusion to hydrogen chemical energy), depending on process conditions

Holistic analysis of thermochemical processes by using solid biomass for fuel production in Germany

International Nuclear Information System (INIS)

Henssler, Martin

2015-01-01

According to the German act ''Biokraftstoff-Nachhaltigkeitsverordnung'', biofuels must show a CO 2eq -reduction compared to the fossil reference fuel (83.8 g CO 2eq /MJ fuel /Richtlinie 98/70/EG/) of 35 % beginning with 2011. In new plants, which go into operation after the 31.12.2016 the CO 2eq -savings must be higher than 50 % in 2017 and higher than 60 % in 2018 /Biokraft-NachV/. The biofuels (methyl ester of rapeseed, bioethanol and biomethane) considered in this study do not meet these requirements for new plants. To comply with these rules new processes must be deployed. Alternative thermochemical generated fuels could be an option. The aim of this work is to evaluate through a technical, ecological and economic analysis (Well-to-Wheel) whether and under what conditions the thermochemical production of Fischer-Tropsch-diesel or -gasoline, hydrogen (H 2 ) and Substitute Natural Gas (SNG) complies with the targets. Four different processes are considered (fast pyrolysis and torrefaction with entrained flow gasifier, CHOREN Carbo-V registered -gasifier, Absorption Enhanced Reforming (AER-) gasifier). Beside residues such as winter wheat straw and residual forest wood, wood from short-rotation plantations is taken into account. The technical analysis showed that at present status (2010) two and in 2050 six plants can be operated energy-self-sufficient. The overall efficiency of the processes is in the range of 41.5 (Fischer-Tropsch-diesel or -gasoline) and 59.4 % (H 2 ). Furthermore, it was found that for 2010, all thermochemical produced fuels except the H 2 -production from wood from short-rotation plantations in decentralised or central fast pyrolysis and in decentralised torrefactions with entrained flow gasifier keep the required CO 2eq -saving of 60 %. In 2050, all thermochemical produced fuels will reach these limits. The CO 2eq -saving is between 72 (H 2 ) and 95 % (Fischer-Tropsch-diesel or -gasoline). When the production costs of the

Achievement report on research and development in the Sunshine Project in fiscal 1976. Research and development of water decomposition by using a hybrid cycle composed of thermo-chemistry and photo-chemistry; 1976 nendo netsukagaku oyobi hikari kagaku hybrid cycle ni yoru mizu bunkai no kenkyu kahatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1977-03-01

This paper describes water decomposition by using a hybrid cycle composed of thermo-chemistry and photo-chemistry. Ferric sulfate and HI are obtained from ferrous sulfate and iodine via photo-chemical reaction. This is an endothermic reaction of 10.8 kcal. Then, the photo-chemically reacted aqueous solution is electrolysed to separate HI, while Fe{sup 3+} (ferric ion) is reduced and converted into Fe{sup 2+} (ferrous ion). Oxygen is generated at this time. Since mixed potential is made from iron oxidation and reduction potential and iodine potential, the electrolytic efficiency is greatly influenced by electrode materials. Ideally, an electrode material that causes only the reduction of Fe{sup 3+}, but not other reactions is preferable. The HI is decomposed into hydrogen and iodine by electrolysis. Research is continuing to acquire hydrogen from HI thermo-chemically. Endothermic reaction heat of 7 to 8 kcal has been obtained in photo-chemical reaction, the heat quantity being close to the theoretical value of 10.8. A result close to the theoretical value may be expected if the electrode material problem is solved. The basic research will be continued for a high possibility of linking the research to a pilot plant in the future. (NEDO)

Utilization of salt ammoniacates in fluidized beds in energy conversion thermochemical systems

International Nuclear Information System (INIS)

Romero, Jesus

1984-01-01

This research thesis notably reports the design and development of a thermochemical storage device involving equilibria of thermal decomposition of ammoniacates of strontium chlorides and calcium chloride in fluidized beds. The experimental study of this device allowed operating conditions and the most important concomitant effects of fluidization to be highlighted. The measured thermal exchange coefficient is about twenty times the measured value in equivalent devices using fixed beds. An irreversibility of the operation has been noticed, and seems to be associated with the irreversible change of grain size of solids. The author also reports a study of the properties of ammoniacates of metallic salts, and of the influence of fluidization on the performance of energy conversion thermochemical systems [fr

Thermochemical equilibrium in a kernel of a UN TRISO coated fuel particle

International Nuclear Information System (INIS)

Kim, Young Min; Jo, C. K.; Lim, H. S.; Cho, M. S.; Lee, W. J.

2012-01-01

A coated fuel particle (CFP) with a uranium mononitride (UN) kernel has been recently considered as an advanced fuel option, such as in fully ceramic micro encapsulated (FCM) replacement fuel for light water reactors (LWRs). In FCM fuel, a large number of tri isotropic coated fuel particles (TRISOs) are embedded in a silicon carbide (SiC) matrix. Thermochemical equilibrium calculations can predict the chemical behaviors of a kernel in a TRISO of FCM fuel during irradiation. They give information on the kind and quantity of gases generated in a kernel during irradiation. This study treats the quantitative analysis of thermochemical equilibrium in a UN TRISO of FCM LWR fuel using HSC software

Solar thermochemical production of ammonia from water, air and sunlight: Thermodynamic and economic analyses

International Nuclear Information System (INIS)

Michalsky, Ronald; Parman, Bryon J.; Amanor-Boadu, Vincent; Pfromm, Peter H.

2012-01-01

Ammonia is an important input into agriculture and is used widely as base chemical for the chemical industry. It has recently been proposed as a sustainable transportation fuel and convenient one-way hydrogen carrier. Employing typical meteorological data for Palmdale, CA, solar energy is considered here as an inexpensive and renewable energy alternative in the synthesis of NH 3 at ambient pressure and without natural gas. Thermodynamic process analysis shows that a molybdenum-based solar thermochemical NH 3 production cycle, conducted at or below 1500 K, combined with solar thermochemical H 2 production from water may operate at a net-efficiency ranging from 23 to 30% (lower heating value of NH 3 relative to the total energy input). Net present value optimization indicates ecologically and economically sustainable NH 3 synthesis at above about 160 tons NH 3 per day, dependent primarily on heliostat costs (varied between 90 and 164 dollars/m 2 ), NH 3 yields (ranging from 13.9 mol% to stoichiometric conversion of fixed and reduced nitrogen to NH 3 ), and the NH 3 sales price. Economically feasible production at an optimum plant capacity near 900 tons NH 3 per day is shown at relative conservative technical assumptions and at a reasonable NH 3 sales price of about 534 ± 28 dollars per ton NH 3 . -- Highlights: ► Conceptual reactant and process improvements of solar-driven NH 3 synthesis at 1 bar. ► Thermodynamic underpinnings of a Molybdenum reactant. ► Process analysis determining energy and materials requirements and the net-efficiency. ► Net present value analysis accounting for yield, investment, and sales price variations.

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

Energy Technology Data Exchange (ETDEWEB)

Gangwal, Santosh [Southern Research Inst., Durham, NC (United States); Muto, Andrew [Southern Research Inst., Durham, NC (United States)

2017-08-30

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 Precision 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 CO₂/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 CO₂ power cycle operating at 200-300 bar pressure and >700°C was determined to be a combination of a diffusion bonded heat

Fuels production by the thermochemical transformation of the biomass

International Nuclear Information System (INIS)

Claudet, G.

2005-01-01

The biomass is a local and renewable energy source, presenting many advantages. This paper proposes to examine the biomass potential in France, the energy valorization channels (thermochemical chains of thermolysis and gasification) with a special interest for the hydrogen production and the research programs oriented towards the agriculture and the forest. (A.L.B.)

Integrated economic and life cycle assessment of thermochemical production of bioethanol to reduce production cost by exploiting excess of greenhouse gas savings

International Nuclear Information System (INIS)

Reyes Valle, C.; Villanueva Perales, A.L.; Vidal-Barrero, F.; Ollero, P.

2015-01-01

Highlights: • Assessment of economics and sustainability of thermochemical ethanol production. • Exploitation of excess CO 2 saving by either importing fossil energy or CO 2 trading. • Significant increase in alcohol production by replacing biomass with natural gas. • CO 2 emission trading is not cost-competitive versus import of fossil energy. • Lowest ethanol production cost for partial oxidation as reforming technology. - Abstract: In this work, two options are investigated to enhance the economics of the catalytic production of bioethanol from biomass gasification by exploiting the excess of CO 2 emission saving: (i) to import fossil energy, in the form of natural gas and electricity or (ii) to trade CO 2 emissions. To this end, an integrated life cycle and economic assessment is carried out for four process configurations, each using a different light hydrocarbon reforming technology: partial oxidation, steam methane reforming, tar reforming and autothermal reforming. The results show that for all process configurations the production of bioethanol and other alcohols significantly increases when natural gas displaces biomass, maintaining the total energy content of the feedstock. The economic advantage of the partial substitution of biomass by natural gas depends on their prices and this is explored by carrying out a sensitivity analysis, taking historical prices into account. It is also concluded that the trade of CO 2 emissions is not cost-competitive compared to the import of natural gas if the CO 2 emission price remains within historical European prices. The CO 2 emission price would have to double or even quadruple the highest CO 2 historical price for CO 2 emission trading to be a cost-competitive option

Thermochemical conversion of biomass in smouldering combustion across scales: The roles of heterogeneous kinetics, oxygen and transport phenomena.

Science.gov (United States)

Huang, Xinyan; Rein, Guillermo

2016-05-01

The thermochemical conversion of biomass in smouldering combustion is investigated here by combining experiments and modeling at two scales: matter (1mg) and bench (100g) scales. Emphasis is put on the effect of oxygen (0-33vol.%) and oxidation reactions because these are poorly studied in the literature in comparison to pyrolysis. The results are obtained for peat as a representative biomass for which there is high-quality experimental data published previously. Three kinetic schemes are explored, including various steps of drying, pyrolysis and oxidation. The kinetic parameters are found using the Kissinger-Genetic Algorithm method, and then implemented in a one-dimensional model of heat and mass transfer. The predictions are validated with thermogravimetric and bench-scale experiments and then analyzed to unravel the role of heterogeneous reaction. This is the first time that the influence of oxygen on biomass smouldering is explained in terms of both chemistry and transport phenomena across scales. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Thermochemical method for the treatment of oil contaminated sand; Metodo termoquimico para tratamento de areia contaminada por oleo

Energy Technology Data Exchange (ETDEWEB)

Pimenta, Rosana C.G.M. [Fundacao Gorceix, Ouro Preto, MG (Brazil)]|[PETROBRAS S.A., Rio de Janeiro, RJ (Brazil); Khalil, Carlos N. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

2004-07-01

In January 2000 there was a major oil spill in Guanabara Bay, Rio de Janeiro, which contaminated 2400 tons of sand. This work, based on NGS (Nitrogen Generating System) technology, was adapted for cleaning contaminated sand and recovering of spilled oil. NGS is a thermochemical method first developed for removal of paraffin deposits in production and export pipelines. The method is based on a strongly exothermic redox chemical reaction between two salts catalyzed in acidic pH. The reaction products are harmless to the environment and consist of nitrogen, sodium chloride, water and heat. By combining simultaneous effects of the treatment such as heating, turbulence and floatation, one can remove, within 98% of efficiency, spilling oil from contaminated sand. After treatment, removed oil can be securely returned to refining process. The method has proved to be efficient, fast, low cost and ecologically correct method for cleaning contaminated sand and can be applied in place right after a contamination event. (author)

Evaluating Indicators and Life Cycle Inventories for Processes in Early Stages of Technical Readiness

Energy Technology Data Exchange (ETDEWEB)

Tan, Eric C [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Smith, Raymond [U.S. Environmental Protection Agency (EPA); Ruiz-Mercado, Gerardo [U.S. Environmental Protection Agency (EPA)

2017-11-01

This presentation examines different methods for analyzing manufacturing processes in the early stages of technical readiness. Before developers know much detail about their processes, it is valuable to apply various assessments to evaluate their performance. One type of assessment evaluates performance indicators to describe how closely processes approach desirable objectives. Another type of assessment determines the life cycle inventories (LCI) of inputs and outputs for processes, where for a functional unit of product, the user evaluates the resources used and the releases to the environment. These results can be compared to similar processes or combined with the LCI of other processes to examine up-and down-stream chemicals. The inventory also provides a listing of the up-stream chemicals, which permits study of the whole life cycle. Performance indicators are evaluated in this presentation with the U.S. Environmental Protection Agency's GREENSCOPE (Gauging Reaction Effectiveness for ENvironmental Sustainability with a multi-Objective Process Evaluator) methodology, which evaluates processes in four areas: Environment, Energy, Economics, and Efficiency. The method develops relative scores for indicators that allow comparisons across various technologies. In this contribution, two conversion pathways for producing cellulosic ethanol from biomass, via thermochemical and biochemical routes, are studied. The information developed from the indicators and LCI can be used to inform the process design and the potential life cycle effects of up- and down-stream chemicals.

Thermochemical investigation of lithium-vanadium bronzes

International Nuclear Information System (INIS)

Filippova, S.E.; Kesler, Ya.A.; Tret'yakov, Yu.D.; Gordeev, I.V.

1979-01-01

A thermochemical investigation was carried out of lithium-vanadium bronzes. The enthalpies of solution and the standard enthalpies of formation of the bronzes β-Lisub(x)Vsub(2)Osub(5) were determined. Investigated was the dependence of the enthalpy of mixing bronzes on the composition; a linear character of the dependence evidences of negligibly small, as compared to the experimental error, energy variations of the matrix V 2 O 5 on introduction of lithium. The variation was calculated of the partial molar enthalpy of lithium in the formation of β-Lisub(x)Vsub(2)Osub(5)

Thermochemical sulphate reduction can improve carbonate petroleum reservoir quality

Science.gov (United States)

Jiang, Lei; Worden, Richard H.; Yang, Changbing

2018-02-01

Interest in the creation of secondary pore spaces in petroleum reservoirs has increased because of a need to understand deeper and more complex reservoirs. The creation of new secondary porosity that enhances overall reservoir quality in deeply buried carbonate reservoirs is controversial and some recent studies have concluded it is not an important phenomenon. Here we present petrography, geochemistry, fluid inclusion data, and fluid-rock interaction reaction modeling results from Triassic Feixianguan Formation, Sichuan Basin, China, core samples and explore the relative importance of secondary porosity due to thermochemical sulphate reduction (TSR) during deep burial diagenesis. We find that new secondary pores result from the dissolution of anhydrite and possibly from dissolution of the matrix dolomite. Assuming porosity before TSR was 16% and the percentage of anhydrite was 6%, modelling shows that, due to TSR, 1.6% additional porosity was created that led to permeability increasing from 110 mD (range 72-168 mD within a 95% confidence interval) to 264 mD (range 162-432 mD within a 95% confidence interval). Secondary porosity results from the density differences between reactant anhydrite and product calcite, the addition of new water during TSR, and the generation of acidity during the reaction of new H2S with the siderite component in pre-existing dolomite in the reservoir. Fluid pressure was high during TSR, and approached lithostatic pressure in some samples; this transient overpressure may have led to the maintenance of porosity due to the inhibition of compactional processes. An additional 1.6% porosity is significant for reserve calculations, especially considering that it occurs in conjunction with elevated permeability that results in faster flow rates to the production wells.

Study on structural design technique of silicon carbide applied for thermochemical hydrogen production IS process

International Nuclear Information System (INIS)

Takegami, Hiroaki; Terada, Atsuhiko; Inagaki, Yoshiyuki; Ishikura, Syuichi

2011-03-01

The IS process is the hydrogen production method which used the thermochemical reaction cycle of sulfuric acid and iodyne. Therefore, the design to endure the high temperature and moreover corrode-able environment is required to the equipment. Specifically, the sulfuric acid decomposer which is one of the main equipment of the IS process is the equipment to heat with hot helium and for the sulfuric acid of 90 wt% to evaporate. Moreover, it is the important equipment to supply the SO 3 decomposer which is the following process, resolving the part of sulfuric acid vapor into SO 3 with. The heat exchanger that sulfuric acid evaporates must be made pressure-resistant structure because it has the high-pressure helium of 4 MPa and the material that the high temperature and the corrosion environment of equal to or more than 700degC can be endured must be used. As the material, it is selected from the corrosion experiment and so on when SiC which is carbonization silicone ceramics is the most excellent material. However, even if it damages the ceramic block which is a heat exchanger because it becomes the structure which is stored in pressure-resistant metallic container, fluid such as sulfuric acid becomes the structure which doesn't leak out outside. However, the structure design technique to have been unified when using ceramics as the structure part isn't serviced as the standard. This report is the one which was studied about the structural design technique to have taken the material strength characteristic of the ceramics into consideration, refer to existing structural design standard. (author)

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

Science.gov (United States)

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...

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

International Nuclear Information System (INIS)

Lee, K.N.; Jacobson, N.S.

1992-01-01

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed. 10 refs

Fiber coating/matrix reactions in silicon-base ceramic matrix composites

Science.gov (United States)

Lee, K. N.; Jacobson, N. S.

1992-01-01

The Knudsen cell technique and coupons of carbon coated Si3N4 and BN coated SiC were employed to study the possible reactions at the SiC/C/Si3N4 and SiC/BN/SiC interface. Carbon reacts with Si3N4 to form gaseous N2 and solid SiC. Solid SiC acts as a physical barrier to the reaction, which prevents the generation of high N2 pressure predicted from thermochemical calculations. Thus, deleterious effects of the reaction to the composite are limited. Limited reactions between BN and C-rich SiC was observed. However, the vapor pressure was so low that it is not likely to cause any interfacial instability. The predicted formation of a BN-C solid solution was not observed.

Life-Cycle Assessment of a Distributed-Scale Thermochemical Bioenergy Conversion System

Science.gov (United States)

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...

Crystal structure and thermochemical properties of 1-decylammonium hydrobromide (C10H21NH3Br)(s)

International Nuclear Information System (INIS)

Zhang Lijun; Di Youying; Lu Dongfei

2011-01-01

Highlights: → Crystal structure of 1-decylammonium hydrobromide was reported. → Lattice potential energy of the compound was obtained. → Molar volumes of the compound and its cation were obtained. → Ionic radius of its cation of the compound was calculated. → Molar enthalpy of dissolution at infinite dilution was determined. → Hydration enthalpies of the compound and its cation were calculated. - Abstract: The crystal structure of 1-decylammonium hydrobromide was determined by X-ray crystallography. Lattice potential energy and molar volumes of the solid compound and its cation were obtained respectively. The ionic radius of the cation can be calculated from the corresponding effective volume of the cation. The molar enthalpies of dissolution of the compound at different concentrations m/(mol . kg -1 ) at T = 298.15 K were measured by an isoperibol solution-reaction calorimeter at T = 298.15 K. According to the Pitzer's electrolyte solution theory, the molar enthalpy of dissolution of the compound at infinite dilution (Δ s H m ∞ ) and Pitzer parameters (β MX (0)L and β MX (1)L ) were obtained. The values of apparent relative molar enthalpies ( Φ L) of the title compound and relative partial molar enthalpies (L 2 -bar and L 1 -bar) of the solute and the solvent at different concentrations were derived from the experimental values of the enthalpy of dissolution of the compound. Finally, hydration enthalpies of the compound and its cation were calculated by designing a thermochemical cycle in accordance with lattice potential energy and the molar enthalpy of dissolution of the title compound at infinite dilution.

Low CO2-emissions hybrid solar combined-cycle power system with methane membrane reforming

International Nuclear Information System (INIS)

Li, Yuanyuan; Zhang, Na; Cai, Ruixian

2013-01-01

Based on the principle of cascade utilization of multiple energy resources, a gas-steam combined cycle power system integrated with solar thermo-chemical fuel conversion and CO 2 capture has been proposed and analyzed. The collected solar heat at 550 °C drives the endothermic methane reforming and is converted to the produced syngas chemical exergy, and then released as high-temperature thermal energy via combustion for power generation, achieving its high-efficiency heat-power conversion. The reforming reaction is integrated with a hydrogen separation membrane, which continuously withdraws hydrogen from the reaction zone and enables nearly full methane conversion. The CO 2 enriched gas being concentrated in the retentate zone is collected and processed with pre-combustion decarbonization. The system is thermodynamically simulated using the ASPEN PLUS code. The results show that with 91% CO 2 captured, the specific CO 2 emission is 25 g/kWh. An exergy efficiency of 58% and thermal efficiency of 51.6% can be obtained. A fossil fuel saving ratio of 31.2% is achievable with a solar thermal share of 28.2%, and the net solar-to-electricity efficiency based on the gross solar heat incident on the collector is about 36.4% compared with the same gas-steam combined cycle system with an equal CO 2 removal ratio obtained by post-combustion decarbonization. - Highlights: ► A solar-assisted hybrid combined cycle power system has been proposed and analyzed. ► The system integrates power generation with solar-driven reforming and CO 2 capture. ► solar heat upgrading and high-efficiency heat-to-power conversion are achieved. ► membrane reforming enables high CH 4 conversion and pre-combustion CO 2 capture. ► The system thermodynamic performances have been investigated and compared

Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

Science.gov (United States)

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.

Coulometric bioelectrocatalytic reactions based on NAD-dependent dehydrogenases in tricarboxylic acid cycle

Energy Technology Data Exchange (ETDEWEB)

Fukuda, Jun [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Tsujimura, Seiya [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)], E-mail: seiya@kais.kyoto-u.ac.jp; Kano, Kenji [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)], E-mail: kkano@kais.kyoto-u.ac.jp

2008-12-30

This paper describes the characterization of mediated electro-enzymatic electrolysis systems based on NAD-dependent dehydrogenase reactions in the tricarboxylic acid (TCA) cycle. A micro-bulk electrolysis system with a carbon felt anode immersed in an electrolysis solution with a value of about 10 {mu}L was constructed for coulometric analysis of the substrate oxidation. Diaphorase (DI) was used to couple the NAD-dependent dehydrogenase reaction with the anode reaction of a suitable redox mediator. We focused on three types of NAD-dependant dehydrogenases reactions in this research: (1) isocitrate oxidation, in which the standard Gibbs energy change ({delta}G{sup o}') is negative; (2) {alpha}-ketoglutarate oxidation, which involves an electrochemically active coenzyme A (CoA); and (3) malate oxidation, which is thermodynamically unfavorable because of a large positive {delta}G{sup o}' value. The complete electrolysis of isocitrate was easily achieved, supporting the effective re-oxidation of NADH in the diaphorase-catalyzed electrochemical reaction. CoA was unfavorably oxidized at the electrodes in the presence of some mediators. The electrocatalytic oxidation of CoA was suppressed and the quantitative electrochemical oxidation of {alpha}-ketoglutarate was achieved by selecting a suitable mediator with negligibly slow electron transfer kinetics with CoA. The uphill malate oxidation was susceptible to product inhibition in the bioelectrochemical system, although NADH generated in the malate dehydrogenase reaction was immediately oxidized in the electrochemical system. The inhibition was successfully suppressed by linking citrate synthase to quench oxaloacetate and to make the total {delta}G{sup o}' value negative.

Coulometric bioelectrocatalytic reactions based on NAD-dependent dehydrogenases in tricarboxylic acid cycle

International Nuclear Information System (INIS)

Fukuda, Jun; Tsujimura, Seiya; Kano, Kenji

2008-01-01

This paper describes the characterization of mediated electro-enzymatic electrolysis systems based on NAD-dependent dehydrogenase reactions in the tricarboxylic acid (TCA) cycle. A micro-bulk electrolysis system with a carbon felt anode immersed in an electrolysis solution with a value of about 10 μL was constructed for coulometric analysis of the substrate oxidation. Diaphorase (DI) was used to couple the NAD-dependent dehydrogenase reaction with the anode reaction of a suitable redox mediator. We focused on three types of NAD-dependant dehydrogenases reactions in this research: (1) isocitrate oxidation, in which the standard Gibbs energy change (ΔG o ') is negative; (2) α-ketoglutarate oxidation, which involves an electrochemically active coenzyme A (CoA); and (3) malate oxidation, which is thermodynamically unfavorable because of a large positive ΔG o ' value. The complete electrolysis of isocitrate was easily achieved, supporting the effective re-oxidation of NADH in the diaphorase-catalyzed electrochemical reaction. CoA was unfavorably oxidized at the electrodes in the presence of some mediators. The electrocatalytic oxidation of CoA was suppressed and the quantitative electrochemical oxidation of α-ketoglutarate was achieved by selecting a suitable mediator with negligibly slow electron transfer kinetics with CoA. The uphill malate oxidation was susceptible to product inhibition in the bioelectrochemical system, although NADH generated in the malate dehydrogenase reaction was immediately oxidized in the electrochemical system. The inhibition was successfully suppressed by linking citrate synthase to quench oxaloacetate and to make the total ΔG o ' value negative

Biomass Program 2007 Program Peer Review - Thermochemical Conversion Platform Summary

Energy Technology Data Exchange (ETDEWEB)

none,

2009-10-27

This document discloses the comments provided by a review panel at the U.S. Department of Energy Office of the Biomass Program Peer Review held on November 15-16, 2007 in Baltimore, MD and the Biomass Program Peer Review for the Thermochemical Platform, held on July 9th and 10th in Golden, Colorado.

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water

International Nuclear Information System (INIS)

Nakajima, Hayato; Imai, Yoshiyuki; Kasahara, Seiji; Kubo, Shinji; Onuki, Kaoru

2007-01-01

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water, which is a unit reaction in the IS process for thermochemical hydrogen production, was studied experimentally at 323 K under iodine saturation. Quasi-equilibrium state was observed in the presence of sulfur dioxide gas at constant pressure. The composition of the poly-hydriodic acid solution formed was discussed assuming an ideal desulfurization by the reverse reaction of the Bunsen reaction. The value of HI/(HI+H 2 O) of the desulfurized solution was large at high sulfur dioxide pressure and reached the maximum of 15.7 ± 0.3 mol%. (author)

Balance and saving of GHG emissions in thermochemical biorefineries

International Nuclear Information System (INIS)

Haro, Pedro; Aracil, Cristina; Vidal-Barrero, Fernando; Ollero, Pedro

2015-01-01

Highlights: • A simplified methodology for the balance and saving of GHG emissions is provided. • The GHG balance has a physical meaning and does not depend on the fossil reference. • The GHG saving depends on regulation of energy carriers. • The impact of Bio-CCS incorporation and multiproduction is analyzed. • The co-production of chemicals needs to be included in future regulation. - Abstract: In this study, a simplified methodology for the calculation of the balance of greenhouse gas (GHG) emissions and corresponding saving compared with the fossil reference is presented. The proposed methodology allows the estimation of the anthropogenic GHG emissions of thermochemical biorefineries (net emitted to the atmosphere). In the calculation of the GHG balance, all relevant factors have been identified and analyzed including multiproduction, emissions from biogenic carbon capture and storage (Bio-CCS), co-feeding of fossil fuels (secondary feedstock) and possible carbon storage in biomass-derived products (chemicals). Therefore, it is possible to calculate the balance of GHG emissions of a hypothetical thermochemical biorefinery considering different alternatives of land-use, biomass feedstock, co-feeding of fossil fuels, Bio-CCS incorporation and final use of the products. The comparison of the estimated GHG balance with the corresponding fossil reference for each product is of special relevance in the methodology since it is the parameter used in European regulation for the fulfillment of sustainability criteria in biomass-derived fuels and liquids. The proposed methodology is tested using a previously assessed set of different process concepts of thermochemical biorefineries (techno-economic analysis). The resulting GHG balance and saving are analyzed to identify uncertainties and provide recommendations for future regulation. In all process concepts, the GHG savings are above the minimum requirement of GHG emissions for 2018. In the case of incorporating

THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

Energy Technology Data Exchange (ETDEWEB)

PROJECT STAFF

2011-10-31

Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature and electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially

A review on the properties of salt hydrates for thermochemical storage

NARCIS (Netherlands)

Trausel, F.; Jong, A.J. de; Cuypers, R.

2014-01-01

Solar energy is capable of supplying enough energy to answer the total demand of energy in dwellings. However, because of the discrepancy between energy supply and energy demand, an efficient way of storing thermal energy is crucial. Thermochemical storage of heat in salt hydrates provides an

Overview of current biological and thermo-chemical treatment technologies for sustainable sludge management.

Science.gov (United States)

Zhang, Linghong; Xu, Chunbao Charles; Champagne, Pascale; Mabee, Warren

2014-07-01

Sludge is a semi-solid residue produced from wastewater treatment processes. It contains biodegradable and recalcitrant organic compounds, as well as pathogens, heavy metals, and other inorganic constituents. Sludge can also be considered a source of nutrients and energy, which could be recovered using economically viable approaches. In the present paper, several commonly used sludge treatment processes including land application, composting, landfilling, anaerobic digestion, and combustion are reviewed, along with their potentials for energy and product recovery. In addition, some innovative thermo-chemical techniques in pyrolysis, gasification, liquefaction, and wet oxidation are briefly introduced. Finally, a brief summary of selected published works on the life cycle assessment of a variety of sludge treatment and end-use scenarios is presented in order to better understand the overall energy balance and environmental burdens associated with each sludge treatment pathway. In all scenarios investigated, the reuse of bioenergy and by-products has been shown to be of crucial importance in enhancing the overall energy efficiency and reducing the carbon footprint. © The Author(s) 2014.

Revisiting dibenzothiophene thermochemical data: Experimental and computational studies

International Nuclear Information System (INIS)

Freitas, Vera L.S.; Gomes, Jose R.B.; Ribeiro da Silva, Maria D.M.C.

2009-01-01

Thermochemical data of dibenzothiophene were studied in the present work by experimental techniques and computational calculations. The standard (p 0 =0.1MPa) molar enthalpy of formation, at T = 298.15 K, in the gaseous phase, was determined from the enthalpy of combustion and sublimation, obtained by rotating bomb calorimetry in oxygen, and by Calvet microcalorimetry, respectively. This value was compared with estimated data from G3(MP2)//B3LYP computations and also with the other results available in the literature.

Exergy analysis of thermochemical ethanol production via biomass gasification and catalytic synthesis

NARCIS (Netherlands)

van der Heijden, H.H.J.L.; Ptasinski, K.J.

2012-01-01

In this paper an exergy analysis of thermochemical ethanol production from biomass is presented. This process combines a steam-blown indirect biomass gasification of woody feedstock, with a subsequent conversion of produced syngas into ethanol. The production process involves several process

Silver nanoclusters-assisted ion-exchange reaction with CdTe quantum dots for photoelectrochemical detection of adenosine by target-triggering multiple-cycle amplification strategy.

Science.gov (United States)

Zhao, Yang; Tan, Lu; Gao, Xiaoshan; Jie, Guifen; Huang, Tingyu

2018-07-01

Herein, we successfully devised a novel photoelectrochemical (PEC) platform for ultrasensitive detection of adenosine by target-triggering cascade multiple cycle amplification based on the silver nanoparticles-assisted ion-exchange reaction with CdTe quantum dots (QDs). In the presence of target adenosine, DNA s1 is released from the aptamer and then hybridizes with hairpin DNA (HP1), which could initiate the cycling cleavage process under the reaction of nicking endonuclease. Then the product (DNA b) of cycle I could act as the "DNA trigger" of cycle II to further generate a large number of DNA s1, which again go back to cycle I, thus a cascade multiple DNA cycle amplification was carried out to produce abundant DNA c. These DNA c fragments with the cytosine (C)-rich loop were captured by magnetic beads, and numerous silver nanoclusters (Ag NCs) were synthesized by AgNO 3 and sodium borohydride. The dissolved AgNCs released numerous silver ions which could induce ion exchange reaction with the CdTe QDs, thus resulting in greatly amplified change of photocurrent for target detection. The detection linear range for adenosine was 1.0 fM ~10 nM with the detection limit of 0.5 fM. The present PEC strategy combining cascade multiple DNA cycle amplification and AgNCs-induced ion-exchange reaction with QDs provides new insight into rapid, and ultrasensitive PEC detection of different biomolecules, which showed great potential for detecting trace amounts in bioanalysis and clinical biomedicine. Copyright © 2018 Elsevier B.V. All rights reserved.

Technology for a Thermo-chemical Ice Penetrator for Icy Moons

Science.gov (United States)

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

2016-10-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Burcat, A.; Ruscic, B.; Chemistry; Technion - Israel Inst. of Tech.

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 on 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.

CATALYSTS NHI Thermochemical Systems FY 2009 Year-End Report

International Nuclear Information System (INIS)

Ginosar, Daniel M.

2009-01-01

Fiscal Year 2009 work in the Catalysts project focused on advanced catalysts for the decomposition of sulfuric acid, a reaction common to both the Sulfur-Iodine (S-I) cycle and the Hybrid Sulfur cycle. Prior years effort in this project has found that although platinum supported on titanium oxide will be an acceptable catalyst for sulfuric acid decomposition in the integrated laboratory scale (ILS) project, the material has short comings, including significant cost and high deactivation rates due to sintering and platinum evaporation. For pilot and larger scale systems, the catalyst stability needs to be improved significantly. In Fiscal Year 2008 it was found that at atmospheric pressure, deactivation rates of a 1 wt% platinum catalyst could be reduced by 300% by adding either 0.3 wt% iridium (Ir) or 0.3 wt% ruthenium (Ru) to the catalyst. In Fiscal Year 2009, work focused on examining the platinum group metal catalysts activity and stability at elevated pressures. In addition, simple and complex metal oxides are known to catalyze the sulfuric acid decomposition reaction. These metal oxides could offer activities comparable to platinum but at significantly reduced cost. Thus a second focus for Fiscal Year 2009 was to explore metal oxide catalysts for the sulfuric acid decomposition reaction. In Fiscal Year 2007 several commercial activated carbons had been identified for the HI decomposition reaction; a reaction specific to the S-I cycle. Those materials should be acceptable for the pilot scale project. The activated carbon catalysts have some disadvantages including low activity at the lower range of reactor operating temperature (350 to 400 C) and a propensity to generate carbon monoxide in the presence of water that could contaminate the hydrogen product, but due to limited funding, this area had low priority in Fiscal Year 2009. Fiscal Year 2009 catalyst work included five tasks: development, and testing of stabilized platinum based H2SO4 catalysts

Kinetics of uncatalyzed thermochemical sulfate reduction by sulfur-free paraffin

Science.gov (United States)

Zhang, Tongwei; Ellis, Geoffrey S.; Ma, Qisheng; Amrani, Alon; Tang, Yongchun

2012-01-01

To determine kinetic parameters of sulfate reduction by hydrocarbons (HC) without the initial presence of low valence sulfur, we carried out a series of isothermal gold-tube hydrous-pyrolysis experiments at 320, 340, and 360 °C under a constant confined pressure of 24.1 MPa. The reactants used consisted of saturated HC (sulfur-free) and CaSO4 in an aqueous solution buffered to three different pH conditions without the addition of elemental sulfur (S8) or H2S as initiators. H2S produced in the course of reaction was proportional to the extent of the reduction of CaSO4 that was initially the only sulfur-containing reactant. Our results show that the in situ pH of the aqueous solution (herein, in situ pH refers to the calculated pH value of the aqueous solution at certain experimental conditions) can significantly affect the rate of the thermochemical sulfate reduction (TSR) reaction. A substantial increase in the TSR reaction rate was observed with a decrease in the in situ pH. Our experimental results show that uncatalyzed TSR is a first-order reaction. The temperature dependence of experimentally measured H2S yields from sulfate reduction was fit with the Arrhenius equation. The determined activation energy for HC (sulfur-free) reacting with View the MathML sourceHSO4− in our experiments is 246.6 kJ/mol at pH values ranging from 3.0 to 3.5, which is slightly higher than the theoretical value of 227.0 kJ/mol using ab initio quantum chemical calculations on a similar reaction. Although the availability of reactive sulfate significantly affects the rate of reaction, a consistent rate constant was determined by accounting for the HSO4− ion concentration. Our experimental and theoretical approach to the determination of the kinetics of TSR is further validated by a reevaluation of several published experimental TSR datasets without the initial presence of native sulfur or H2S. When the effect of reactive sulfate concentration is appropriately accounted for, the

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

Directory of Open Access Journals (Sweden)

Robert Pitz-Paal

2012-10-01

Full Text Available 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.

Applicability test of glass lining material for high-temperature acidic solutions of sulfuric acid in thermochemical water-splitting IS process

International Nuclear Information System (INIS)

Iwatsuki, Jin; Tanaka, Nobuyuki; Terada, Atsuhiko; Onuki, Kaoru; Watanabe, Yutaka

2010-01-01

A key issue for realizing the thermochemical IS process for hydrogen production is the selection of materials for working with high-temperature acidic solutions of sulfuric acid and hydriodic acid. Glass lining material is a promising candidate, which is composed of steel having good strength and glass having good corrosion resistance. Since the applicability of glass lining material depends strongly on the service condition, corrosion tests using glass used in glass lining material and heat cycle tests using glass lining piping were carried out to examine the possibility of using the glass lining material with high-temperature acidic solutions of sulfuric acid. It was confirmed that the glass lining materials exhibited sufficient corrosion resistance and heat resistance in high-temperature sulfuric acid of the IS process. (author)

Thermochemical study of deuterium exchange reactions in water-alcohol and alcohol-alcohol systems

International Nuclear Information System (INIS)

Khurma, J.R.; Fenby, D.V.

1979-01-01

Molar excess enthalpies of water-alcohol systems have been analyzed to give equilibrium constants and enthalpies of the reactions 2ROH + D 2 O = 2ROD + H 2 O (R = CH 3 , C 2 H 5 , n-C 3 H 7 ). The equilibrium constants are significantly greater than the ''random'' value. Molar excess enthalpies of alcohol-alcohol systems have been analyzed to give enthalpies of reactions ROH + R'OD = ROD + R'OH. The enthalpies of water-alcohol and alcohol-alcohol exchange reactions form a self-consistent set and are in good agreement with values from earlier studies. Molar excess enthalpies at 298.15 K are reported for n-C 3 H 7 OH and n-C 3 H 7 OD with H 2 O, D 2 O, CH 3 OH, CH 3 OD, C 2 H 5 OH, and C 2 H 5 OD

Solar fuel processing efficiency for ceria redox cycling using alternative oxygen partial pressure reduction methods

International Nuclear Information System (INIS)

Lin, Meng; Haussener, Sophia

2015-01-01

Solar-driven non-stoichiometric thermochemical redox cycling of ceria for the conversion of solar energy into fuels shows promise in achieving high solar-to-fuel efficiency. This efficiency is significantly affected by the operating conditions, e.g. redox temperatures, reduction and oxidation pressures, solar irradiation concentration, or heat recovery effectiveness. We present a thermodynamic analysis of five redox cycle designs to investigate the effects of working conditions on the fuel production. We focused on the influence of approaches to reduce the partial pressure of oxygen in the reduction step, namely by mechanical approaches (sweep gassing or vacuum pumping), chemical approaches (chemical scavenger), and combinations thereof. The results indicated that the sweep gas schemes work more efficient at non-isothermal than isothermal conditions, and efficient gas phase heat recovery and sweep gas recycling was important to ensure efficient fuel processing. The vacuum pump scheme achieved best efficiencies at isothermal conditions, and at non-isothermal conditions heat recovery was less essential. The use of oxygen scavengers combined with sweep gas and vacuum pump schemes further increased the system efficiency. The present work can be used to predict the performance of solar-driven non-stoichiometric redox cycles and further offers quantifiable guidelines for system design and operation. - Highlights: • A thermodynamic analysis was conducted for ceria-based thermochemical cycles. • Five novel cycle designs and various operating conditions were proposed and investigated. • Pressure reduction method affects optimal operating conditions for maximized efficiency. • Chemical oxygen scavenger proves to be promising in further increasing efficiency. • Formulation of quantifiable design guidelines for economical competitive solar fuel processing

JAEA’s R&D on the Thermochemical Hydrogen Production IS Process

International Nuclear Information System (INIS)

Kasahara, Seiji; Tanaka, Nobuyuki; Noguchi, Hiroki; Iwatsuki, Jin; Takegami, Hiroaki; Yan, Xing L.; Kubo, Shinji

2014-01-01

Japan Atomic Energy Agency (JAEA) has studied iodine-sulfur (IS) process, a thermochemical cycle to produce hydrogen by water splitting. This process is a candidate application of high temperature heat from high temperature gas-cooled reactors. This paper outlines the IS process study in JAEA, in particular recent situation of the R&D. Reactor components and a total process facility are tested to evaluate their integrity. A Bunsen reactor, a H_2SO_4 decomposer and a HI decomposer made of industrial materials such as SiC ceramic, fluoroplastic and lining materials have been examined separately as reactor components. A semibatch test and a thermal cycle test were operated in the Bunsen reactor. H_2SO_4 decomposition test is in a bayonet type reactor and HI decomposition test in an adiabatic radial flow type reactor are now under way. On the basis of a demonstration of continuous hydrogen production of 31 NL/h by a glass apparatus, an experimental apparatus of the total IS process has just been constructed to verify integrity of process components of industrial materials, H_2 production scale of which is 200 NL/h. Electro-electrodialysis (EED) cells to concentrate HI before distillation and a SiC-made bayonet type H_2SO_4 decomposer are applied in the facility. Process data of EED cells has been collected aiming to improve H_2 production thermal efficiency. Influence of temperature, composition in solution and existence of impurities on the cell properties has been investigated. Reduction of heat input to a HI separation step by applying the results of the study was shown. (author)

Influence of material choice on cost estimation of some key components of the Sulfur Iodine thermochemical process

International Nuclear Information System (INIS)

Gilardi, T.; Rodriguez, G.; Gomez, A.; Leybros, J.; Borgard, J.M.; Carles, P.; Anzieu, P.

2006-01-01

In the frame of the preliminary design of an sulfur/iodine thermochemical plant coupled with a 600 MWth Helium cooled High Temperature Reactor, CEA has pre-designed all the components of the I/S plant and has started to the cost estimation of all the key components with some industrial cost evaluation methods proposed by CHAUVEL or PETER and TIMMERHAUS. The purpose of the paper is to present the strong influence of material choice on final cost estimation of these key components by comparing price with standard material (steel) and the most appropriate material selected to support the strong corrosion involved by several chemical reactions of the I/S process. These results reinforce the fact that material selection must be done with the best accuracy and that it will be a key factor in the global economy of these plant investment. (authors)

Resonant elastic scattering of 15O and a new reaction path in the CNO cycle

International Nuclear Information System (INIS)

Stefan, Gheorghe Iulian

2006-12-01

the reaction products from beam particles. The separation is based on the magnetic rigidity values different for the nuclei composing the beam from the ones of the reaction products under study. The new results obtained were confronted with the computed rate of the reaction 15 O(p,β + ) 16 O in comparison with the rate estimations for 15 O(α,γ) 19 Ne. For the first time one underlines the significance of the low energy tail of a resonance in an unbound nucleus. The effect would be an enhancement of the beta decay of 16 F. The consequences for astrophysical processes are underlined. New sequential reactions are suggested and two new reaction cycles from 15 O trough again 15 O are described on this basis. These newly suggested cycles can enhance the energy generation in an explosive environment. To study thoroughly their influence these two new cycles should be introduced in advanced simulation astrophysical codes particularly into those simulating the X bursts

Measurement from sun-synchronous orbit of a reaction rate controlling the diurnal NOx cycle in the stratosphere

Directory of Open Access Journals (Sweden)

A. Dudhia

2011-05-01

Full Text Available A reaction rate associated with the nighttime formation of an important diurnally varying species, N2O5, is determined from MIPAS-ENVISAT. During the day, photolysis of N2O5 in the stratosphere contributes to nitrogen-catalysed ozone destruction. However, at night concentrations of N2O5 increase, temporarily sequestering reactive NOx NO and NO2 in a natural cycle which regulates the majority of stratospheric ozone. In this paper, the reaction rate controlling the formation of N2O5 is determined from this instrument for the first time. The observed reaction rate is compared to the currently accepted rate determined from laboratory measurements. Good agreement is obtained between the observed and accepted experimental reaction rates within the error bars.

Thermo-chemical simulation of a composite offshore vertical axis wind turbine blade

DEFF Research Database (Denmark)

Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

2012-01-01

In the present study three dimensional steady state thermo-chemical simulation of a pultrusion process is investigated by using the finite element/nodal control volume (FE/NCV) technique. Pultrusion simulation of a composite having a C-shaped cross section is performed as a validation case. The o...

Thermo-chemical simultion of a composite offshore vertical axis wind turbine blade

NARCIS (Netherlands)

Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

2012-01-01

In the present study three dimensional steady state thermo-chemical simulation of a pultrusion process is investigated by using the finite element/nodal control volume (FE/NCV) technique. Pultrusion simulation of a composite having a C-shaped cross section is performed as a validation case. The

Determination of standard molar enthalpies of formation of SrMoO4 micro/nano structures

International Nuclear Information System (INIS)

Guo, Yunxiao; Fan, Gaochao; Huang, Zaiyin; Sun, Jilong; Wang, Lude; Wang, Tenghui; Chen, Jie

2012-01-01

Graphical abstract: Schematic illustration of thermochemical cycle between the nano and bulk reaction systems. Highlights: ► A thermochemical cycle was designed. ► Relationship of standard molar enthalpies of formation between micro/nano and bulk SrMoO 4 was gained. ► Microcalorimetry was used as a supplementary technology. ► Standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 were obtained. ► This novel approach can be used to other micro/nano materials. - Abstract: SrMoO 4 micro/nano structures were prepared by a simple reverse microemulsion method and were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscope (SEM). In order to associate standard molar enthalpies of formation of nano SrMoO 4 with bulk SrMoO 4 , the relationship of them was obtained through designing a thermochemical cycle according to thermodynamic potential function method. Combined with microcalorimetry, the standard molar enthalpies of formation of the synthesized micro/nano SrMoO 4 at 298.15 K were gained in this paper. And the variation of standard molar enthalpies of formation of micro/nano SrMoO 4 with different morphologies and sizes was discussed.

Copper oxide--copper sulfate water-splitting cycle

Energy Technology Data Exchange (ETDEWEB)

Foh, S. E.; Schreiber, J. D.; Dafler, J. R.

1978-08-01

A hybrid copper oxide--copper sulfate thermochemical water-splitting cycle, IGT's H-5, has been demonstrated in the laboratory with recycled materials. The optimum configuration and operating conditions for the electrolytic hydrogen-producing step have not yet been defined. With cooperative funding (A.G.A./G.R.I./DOE) a conceptual flowsheet was developed for this cycle and a load-line efficiency of about 37% calculated. This figure is the result of a single iteration on the original base case flow sheet and compares well with the values calculated for other processes at this stage of development. An iterative optimization of process conditions would improve efficiency. The data required to perform an economic analysis are not yet available and the electrolysis step must be more fully defined. An attractive process efficiency, relatively few corrosive materials, and few gas-phase separations are attributes of Cycle H-5 that lead us to believe hydrogen costs (to be developed during future analyses) would be improved significantly over similar processes analyzed to date.

Thermochemical parameters of minerals from oxygen-buffered hydrothermal equilibrium data: Method, application to annite and almandine

Science.gov (United States)

Zen, E.-A.

1973-01-01

Reversed univariant hydrothermal phase-equilibrium reactions, in which a redox reaction occurs and is controlled by oxygen buffers, can be used to extract thermochemical data on minerals. The dominant gaseous species present, even for relatively oxidizing buffers such as the QFM buffer, are H2O and H2; the main problem is to calculate the chemical potentials of these components in a binary mixture. The mixing of these two species in the gas phase was assumed by Eugster and Wones (1962) to be ideal; this assumption allows calculation of the chemical potentials of the two components in a binary gas mixture, using data in the literature. A simple-mixture model of nonideal mixing, such as that proposed by Shaw (1967), can also be combined with the equations of state for oxygen buffers to permit derivation of the chemical potentials of the two components. The two mixing models yield closely comparable results for the more oxidizing buffers such as the QFM buffer. For reducing buffers such as IQF, the nonideal-mixing correction can be significant and the Shaw model is better. The procedure of calculation of mineralogical thermochemical data, in reactions where hydrogen and H2O simultaneously appear, is applied to the experimental data on annite, given by Wones et al. (1971), and on almandine, given by Hsu (1968). For annite the results are: Standard entropy of formation from the elements, Sf0 (298, 1)=-283.35??2.2 gb/gf, S0 (298, 1) =+92.5 gb/gf. Gf0 (298, 1)=-1148.2??6 kcal, and Hf0 (298, 1)=-1232.7??7 kcal. For almandine, the calculation takes into account the mutual solution of FeAl2O4 (Hc) in magnetite and of Fe3O4 (Mt) in hercynite and the temperature dependence of this solid solution, as given by Turnock and Eugster (1962); the calculations assume a regular-solution model for this binary spinel system. The standard entropy of formation of almandine, Sf,A0 (298, 1) is -272.33??3 gb/gf. The third law entropy, S0 (298, 1) is +68.3??3 gb/gf, a value much less than the

Thermodynamics of coproportionation reactions of homogeneous samarium (3) and yttrium (3) nitrates solvates with neutral organic phosphorus compounds

International Nuclear Information System (INIS)

Pyartman, A.K.

1995-01-01

Reaction heats of homogeneous samarium (3) and yttrium (3) nitrate solvates coproportionation with neutral organophosphoric compounds (tri-n.-butylphosphate, diisooctylmethylphosphonate, diisoamylmethylphosphonate) at T=298.15 K in hexane have been measured by thermochemical method. It has been ascertained that enthalpies of coproportionation reactions practically do not depend on the nature, concentration of rare earth metal (3) nitrate solvates in hexane, nature of neutral organophosphoric compound and constitute 1.1±-.2 kJ/mol. The Gibbs free energy of coproportionation reactions is -5.43 kJ/mol, while entropy of the reactions in 14.5±0.7 J/mol·K. 8 refs., 1 tab

Splitting CO2 with a ceria‐based redox cycle in a solar‐driven thermogravimetric analyzer

Science.gov (United States)

Takacs, M.; Ackermann, S.; Bonk, A.; Neises‐von Puttkamer, M.; Haueter, Ph.; Scheffe, J. R.; Vogt, U. F.

2016-01-01

Thermochemical splitting of CO2 via a ceria‐based redox cycle was performed in a solar‐driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr4+‐doped CeO2, were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200–1950 K and subsequently re‐oxidized with CO2 at 950–1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm‐sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm‐sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr4+‐doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1263–1271, 2017 PMID:28405030

Splitting CO2 with a ceria-based redox cycle in a solar-driven thermogravimetric analyzer.

Science.gov (United States)

Takacs, M; Ackermann, S; Bonk, A; Neises-von Puttkamer, M; Haueter, Ph; Scheffe, J R; Vogt, U F; Steinfeld, A

2017-04-01

Thermochemical splitting of CO 2 via a ceria-based redox cycle was performed in a solar-driven thermogravimetric analyzer. Overall reaction rates, including heat and mass transport, were determined under concentrated irradiation mimicking realistic operation of solar reactors. Reticulated porous ceramic (RPC) structures and fibers made of undoped and Zr 4+ -doped CeO 2 , were endothermally reduced under radiative fluxes of 1280 suns in the temperature range 1200-1950 K and subsequently re-oxidized with CO 2 at 950-1400 K. Rapid and uniform heating was observed for 8 ppi ceria RPC with mm-sized porosity due to its low optical thickness and volumetric radiative absorption, while ceria fibers with μm-sized porosity performed poorly due to its opacity to incident irradiation. The 10 ppi RPC exhibited higher fuel yield because of its higher sample density. Zr 4+ -doped ceria showed increasing reduction extents with dopant concentration but decreasing specific CO yield due to unfavorable oxidation thermodynamics and slower kinetics. © 2016 American Institute of Chemical Engineers , 63: 1263-1271, 2017.

Effect of multiple-feedstock strategy on the economic and environmental performance of thermochemical ethanol production under extreme weather conditions

International Nuclear Information System (INIS)

Kou, Nannan; Zhao, Fu

2011-01-01

Current US transportation sector mainly relies on liquid hydrocarbons derived from petroleum and about 60% of the petroleum consumed is from areas where supply may be disturbed by regional instability. This has led to serious concerns on energy security and global warming. To address these issues, numerous alternative energy carriers have been proposed. Among them, second generation biofuel is one of the most promising technologies. Gasification-based thermochemical conversion will bring flexibility to both feedstock and production sides of a plant, thus presents an attractive technical route to address both the energy security and global warming concerns. In this paper, thermochemical ethanol production using multiple-feedstock (corn stover, municipal solid waste, and wood chips) is simulated using Aspen Plus and compared with the single-feedstock scenario, in terms of economic performances, life cycle greenhouse gas (GHG) emissions and survivability under extreme weather conditions. For a hypothetical facility in southwest Indiana it is found that multiple-feedstock strategy improves the net present value by 18% compared to single-feedstock strategy. This margin is increased to 57% when effects of extreme weather conditions on feedstock supply are considered. Moreover, multiple-feedstock fuel plant has no potential risk of bankruptcy during the payback period, while single-feedstock fuel plant has a 75% chance of bankruptcy. Although the multiple-feedstock strategy has 26% more GHG emission per liter of ethanol produced than the single-feedstock strategy, the trend is reversed if feedstock supply disruption is taken into account. Thus the idea of multiple-feedstock strategy is proposed to the future thermo chemical biofuel plants.

Thermochemical liquefaction characteristics of microalgae in sub- and supercritical ethanol

Energy Technology Data Exchange (ETDEWEB)

You, Qiao; Chen, Liang [College of Environmental Science and Engineering, Hunan University, Changsha (China); Key Laboratory of Environment Biology and Pollution Control, Ministry of Education, Changsha (China)

2011-01-15

Thermochemical liquefaction characteristics of Spirulina, a kind of high-protein microalgae, were investigated with the sub- and supercritical ethanol as solvent in a 1000 mL autoclave. The influences of various liquefaction parameters on the yields of products (bio-oil and residue) from the liquefaction of Spirulina were studied, such as the reaction temperature (T), the S/L ratio (R{sub 1}, solid: Spirulina, liquid: ethanol), the solvent filling ratio (R{sub 2}) and the type and dosage of catalyst. Without catalyst, the bio-oil yields were in the range of 35.4 wt.% and 45.3 wt.% depending on the changes of T, R{sub 1} and R{sub 2}. And the bio-oil yields increased generally with increasing T and R{sub 2}, while the bio-oil yields reduced with increasing R{sub 1}. The FeS catalyst was certified to be an ideal catalyst for the liquefaction of Spirulina microalgae for its advantages on promoting bio-oil production and suppressing the formation of residue. The optimal dosage of catalyst (FeS) was ranging from 5-7 wt.%. The elemental analyses and FT-IR and GC-MS measurements for the bio-oils revealed that the liquid products have much higher heating values than the crude Spirulina sample and fatty acid ethyl ester compounds were dominant in the bio-oils, irrespective of whether catalyst was used. (author)

Recommended Ideal-Gas Thermochemical Functions for Heavy Water and its Substituent Isotopologues

Czech Academy of Sciences Publication Activity Database

Simkó, I.; Furtenbacher, T.; Hrubý, Jan; Zobov, N. F.; Polyansky, O. L.; Tennyson, J.; Gamache, R. R.; Szidarovszky, T.; Dénes, N.; Császár, A. G.

2017-01-01

Roč. 46, č. 2 (2017), č. článku 023104. ISSN 0047-2689 R&D Projects: GA ČR GA16-02647S Institutional support: RVO:61388998 Keywords : heavy water * ideal-gas thermochemical functions * partition function Subject RIV: BJ - Thermodynamics OBOR OECD: Thermodynamics Impact factor: 4.204, year: 2016

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

DEFF Research Database (Denmark)

Gunnarsson, Ingólfur Bragi; Kuglarz, Mariusz; Karakashev, Dimitar Borisov

2015-01-01

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 (21.9gL-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....

The coupling effect of gas-phase chemistry and surface reactions on oxygen permeation and fuel conversion in ITM reactors

KAUST Repository

Hong, Jongsup

2015-08-01

© 2015 Elsevier B.V. The effect of the coupling between heterogeneous catalytic reactions supported by an ion transport membrane (ITM) and gas-phase chemistry on fuel conversion and oxygen permeation in ITM reactors is examined. In ITM reactors, thermochemical reactions take place in the gas-phase and on the membrane surface, both of which interact with oxygen permeation. However, this coupling between gas-phase and surface chemistry has not been examined in detail. In this study, a parametric analysis using numerical simulations is conducted to investigate this coupling and its impact on fuel conversion and oxygen permeation rates. A thermochemical model that incorporates heterogeneous chemistry on the membrane surface and detailed chemical kinetics in the gas-phase is used. Results show that fuel conversion and oxygen permeation are strongly influenced by the simultaneous action of both chemistries. It is shown that the coupling somewhat suppresses the gas-phase kinetics and reduces fuel conversion, both attributed to extensive thermal energy transfer towards the membrane which conducts it to the air side and radiates to the reactor walls. The reaction pathway and products, in the form of syngas and C2 hydrocarbons, are also affected. In addition, the operating regimes of ITM reactors in which heterogeneous- or/and homogeneous-phase reactions predominantly contribute to fuel conversion and oxygen permeation are elucidated.

Resonant elastic scattering of {sup 15}O and a new reaction path in the CNO cycle; Spectroscopie par diffusion elastique resonante d' {sup 15}O et nouveau chemin de reaction dans le cycle CNO

Energy Technology Data Exchange (ETDEWEB)

Stefan, Gheorghe Iulian [Ecole doctorale SIMEM, U.F.R. Sciences, Universite de Caen Basse-Normandie, 14032 Caen Cedex (France)

2006-12-15

direction. There are stressed the advantages of this approach and one gives details concerning the method of separation of the reaction products from beam particles. The separation is based on the magnetic rigidity values different for the nuclei composing the beam from the ones of the reaction products under study. The new results obtained were confronted with the computed rate of the reaction {sup 15}O(p,{beta}{sup +}){sup 16}O in comparison with the rate estimations for {sup 15}O({alpha},{gamma}){sup 19}Ne. For the first time one underlines the significance of the low energy tail of a resonance in an unbound nucleus. The effect would be an enhancement of the beta decay of {sup 16}F. The consequences for astrophysical processes are underlined. New sequential reactions are suggested and two new reaction cycles from {sup 15}O trough again {sup 15}O are described on this basis. These newly suggested cycles can enhance the energy generation in an explosive environment. To study thoroughly their influence these two new cycles should be introduced in advanced simulation astrophysical codes particularly into those simulating the X bursts.

Prediction of Mechanism and Thermochemical Properties of O3 + H2S Atmospheric Reaction

Directory of Open Access Journals (Sweden)

Morteza Vahedpour

2013-01-01

Full Text Available Ozone and hydrogen sulfide reaction mechanism including a complex was studied at the B3LYP/6-311++G(3df,3pd and CCSD/6-311++G(3df,3pd//B3LYP/6-311++G(3df,3pd levels of computation. The interaction between sulfur atom of hydrogen sulfide and terminal oxygen atom of ozone produces a stable H2S-O3 complex with no barrier. With the decomposition of this complex, four possible product channels have been found. Intrinsic reaction coordinate, topological analyses of atom in molecule, and vibrational frequency calculation have been used to confirm the suggested mechanism. Thermodynamic data at T = 298.15 K and the atmospheric pressure have been calculated. The results show that the production of H2O + SO2 is the main reaction channel with ΔG° = −645.84 kJ/mol. Rate constants of H2S + O3 reaction show two product channels, SO2 + H2O and HSO + HOO, which compete with each other based on the temperature.

To Error Problem Concerning Measuring Concentration of Carbon Oxide by Thermo-Chemical Sen

Directory of Open Access Journals (Sweden)

V. I. Nazarov

2007-01-01

Full Text Available The paper gives additional errors in respect of measuring concentration of carbon oxide by thermo-chemical sensors. A number of analytical expressions for calculation of error data and corrections for environmental factor deviations from admissible ones have been obtained in the paper

Thermochemical and thermophysical properties of alkaline-earth perovskites

International Nuclear Information System (INIS)

Yamanaka, Shinsuke; Kurosaki, Ken; Maekawa, Takuji; Matsuda, Tetsushi; Kobayashi, Shin-ichi; Uno, Masayoshi

2005-01-01

In order to contribute to safety evaluation of high burnup oxide fuels, we studied the thermochemical and thermophysical properties of alkaline-earth perovskites known as oxide inclusions. Polycrystalline samples of alkaline-earth perovskites, BaUO 3 , BaZrO 3 , BaCeO 3 , BaMoO 3 , SrTiO 3 , SrZrO 3 , SrCeO 3 , SrMoO 3 , SrHfO 3 and SrRuO 3 , were prepared and the thermal expansion coefficient, melting temperature, elastic moduli, Debye temperature, microhardness, heat capacity, and thermal conductivity were measured. The relationship between some physical properties was studied

Breakout from the hot CNO cycle: the {sup 15}O({alpha},{gamma}) and {sup 18}Ne({alpha},p) reactions

Energy Technology Data Exchange (ETDEWEB)

Bradfield-Smith, W; Laird, A M; Davinson, T; Pietro, A di; Ostrowski, A N; Shotter, A C; Woods, P J [Dept. of Physics and Astronomy, Univ. of Edinburgh (United Kingdom); Cherubini, S; Galster, W; Graulich, J S; Leleux, P; Michel, L; Ninane, A; Vervier, J [Inst. de Physique Nucleaire, UCL, Louvain-la-Neuve (Belgium); Aliotta, M; Cali, D; Cappussello, F; Cunsolo, A; Spitaleri, C [INFN, Catania (Italy); Gorres, J; Wiescher, M [Notre Dame Univ. (United States); Rahighi, J [Van de Graaf Lab., Tehran (Iran, Islamic Republic of); Hinnefeld, J [Indiana Univ., South Bend (United States)

1998-06-01

One of the most important reactions which determines the rate of breakout from the hot CNO cycle is the {sup 15}O({alpha},{gamma}){sup 19}Ne. The reaction {sup 18}Ne({alpha},p){sup 21}Na may also provide an alternative breakout route. Experiments are being undertaken at Louvain-La-Neuve using the radioactive {sup 18}Ne beam to study these reactions by measurement of {alpha}({sup 18}Ne,p){sup 21}Na and d({sup 18}Ne,p){sup 19}Ne{sup *} {yields} {sup 15}O + {alpha} (orig.)

Solar processing of CO2 and H2O, routes for solar fuels

International Nuclear Information System (INIS)

Flammant, G.; Abanades, St.

2008-01-01

Complete text of publication follows: Concentrated solar energy provides heat in the temperature range 200 C - 3000 C for concentration ratio variation from 10 to 10 000 (three orders of magnitude). Consequently, solar-driven thermochemical processes may be proposed to produce hydrogen from water decomposition and to reduce carbon dioxide. This lecture gives an overview of such processes. High temperature thermochemical cycles for hydrogen production by water splitting are currently studied at PROMES lab, particularly 2-step and 3-step cycles based on the following reaction scheme, MOox → MOred + 1/2 O 2 (high temperature solar step), MOred + H 2 O → MOox + H 2 (low temperature non solar step). Volatile and non-volatile oxide cycles are developed from the chemical and the engineering points of view. A similar reaction scheme may be proposed to reduce carbon dioxide with concentrated solar energy (Fig. 1), it comes, MOox → MOred + 1/2 O 2 (high temperature solar step), MOred + CO 2 → MOox + CO (low temperature non solar step). As a result gas mixtures such as CO 2 /H 2 and CO/H 2 may be produced by solar energy. Such mixtures are the reactants for liquid fuels production (solar fuels)

A gas dynamic and thermochemical model of steam/sodium microleak phenomena

International Nuclear Information System (INIS)

Perkins, R.; Airey, R.; Daniels, L.C.

1985-06-01

Conflicting findings have been reported by 3 UK laboratories for the blockage or rapid escalation of steam/sodium microleaks. In an earlier paper it was shown that this discrepancy could be resolved through the influence on the steam flow of the geometry of the leak paths; the geometry being dependent upon the method of manufacture. The application of gas dynamics and thermochemical methods could account for the rapid escalation of some leaks in terms of the presence of shock waves in the gas flow within the leak path. In this paper the gas dynamic and thermochemical theories are re-stated and a series of leak experiments conducted to test the validity of the theory is described. The theory predicts that for some leaks of variable area of cross-section the blockage/escalation behaviour is determined by small changes in the sodium-side pressure; this effect was found and is discussed as a validation of the theory. Other aspects of leak phenomena are discussed and conclusions are drawn with emphasis on implications for further programmes of leak study and for leaks in LMFBR steam generators in service. (author)

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Yoon, Ho Joon

2010-02-15

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H{sub 2}O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I{sub 2}/H{sub 2}SO{sub 4} in the feed increased from 2 to 4, the molar ratio of HI/(HI+H{sub 2}O) in the HI{sub x} phase improved from 0.157 to 0.22, which

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

International Nuclear Information System (INIS)

Yoon, Ho Joon

2010-02-01

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H 2 O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I 2 /H 2 SO 4 in the feed increased from 2 to 4, the molar ratio of HI/(HI+H 2 O) in the HI x phase improved from 0.157 to 0.22, which is high enough to generate

A pilot test plan of the thermochemical water-splitting iodine-sulfur process

International Nuclear Information System (INIS)

Kubo, Shinji; Kasahara, Seiji; Okuda, Hiroyuki; Terada, Atsuhiko; Tanaka, Nobuyuki; Inaba, Yoshitomo; Ohashi, Hirofumi; Inagaki, Yoshiyuki; Onuki, Kaoru; Hino, Ryutaro

2004-01-01

Research and development (R and D) of hydrogen production systems using high-temperature gas-cooled reactors (HTGR) are being conducted by the Japan Atomic Research Institute (JAERI). To develop the systems, superior hydrogen production methods are essential. The thermochemical hydrogen production cycle, the IS (iodine-sulfur) process, is a prospective candidate, in which heat supplied by HTGR can be consumed for the thermal driving load. With this attractive feature, JAERI will conduct pilot-scale tests, aiming to establish technical bases for practical plant designs using HTGR. The hydrogen will be produced at a maximum rate of 30 m 3 /h, continuously using high-temperature helium gas supplied by a helium gas loop, with an electric heater of about 400 kW. The plant will employ an advanced hydroiodic acid-processing device for efficient hydrogen production, and the usefulness of the device was confirmed from mass and heat balance analysis. Through design works and the hydrogen production tests, valuable data for construction and operation will be acquired to evaluate detailed process performance for practical systems. After completing the pilot-scale tests, JAERI will move onto the next R and D step, which will be demonstrations of the IS process to which heat is supplied from a high-temperature engineering test reactor (HTTR)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

Thermodynamic comparison of two processes of hydrogen production: steam methane reforming-A solar thermochemical process

International Nuclear Information System (INIS)

Gomri, Rabah; Boumaza, Mourad

2006-01-01

Hydrogen is mainly employed like primary product, for the synthesis of ammonia. The ammonia is synthesized by chemically combining hydrogen and nitrogen under pressure, in the presence of a catalyst. This ammonia is used, for the production of the nitrate fertilizers. Nowadays hydrogen gains more attention mainly because, it is regarded as a future significant fuel by much of experts. The widespread use of hydrogen as source of energy could help to reduce the concern concerning the safety of energy, the total change of climate and the quality of air. Hydrogen is presented then as an excellent alternate initially and as substitute thereafter. It can play a role even more significant than conventional energies. Indeed, it has the advantage of being nonpolluting and it can use the same means of transport as conventional energies. For Algeria, it proves of importance capital. It not only makes it possible to increase and diversify its energy reserves and its exports but also to provide for its energy needs which become increasingly significant. Although hydrogen can be produced starting from a large variety of resources using a range of various technologies, the natural gas is generally preferred and will remain in the near future the principal primary product for the manufacture of hydrogen. Currently the most effective means of production of hydrogen is the Steam Reforming of Natural Gas (SMR). This process is seen as a one of principal technologies for the production of hydrogen. The disadvantages of this process it's that it consumes a great quantity of primary energy and that it releases in the atmosphere the gases that contribute to the warming of the plane. Among the alternatives processes of hydrogen production one can quote solar thermochemical processes. In this study, an exergetic analysis of the process of hydrogen production based on Zn/ZnO redox reactions is presented. In the first part of this study, an exergetic analysis is made for a temperature of the

Effects of ultrasonic and thermo-chemical pre-treatments on methane production from fat, oil and grease (FOG) and synthetic kitchen waste (KW) in anaerobic co-digestion.

Science.gov (United States)

Li, Chenxi; Champagne, Pascale; Anderson, Bruce C

2013-02-01

The effects of ultrasonic and thermo-chemical pre-treatments on the methane production potential of anaerobic co-digestion with synthetic kitchen waste (KW) or fat, oil and grease (FOG) were investigated. Non-linear regressions were fitted to accurately assess and compare the methane production from co-digestion under the various pre-treatment conditions and to achieve representative simulations and predictions. Ultrasonic pre-treatment was not found to improve methane production effectively from either FOG co-digestion or KW co-digestions. Thermo-chemical pre-treatment could increase methane production yields from both FOG and KW co-digestions. COD solubilization was found to effectively represent the effects of pre-treatment. A comprehensive evaluation indicated that the thermo-chemical pre-treatments of pH=10, 55°C and pH=8, 55°C provided the best conditions to increase methane production from FOG and KW co-digestions, respectively. The most effective enhancement of biogas production (288±0.85mLCH(4)/g TVS) was achieved from thermo-chemically pre-treated FOG co-digestion, which was 9.9±1.5% higher than FOG co-digestion without thermo-chemical pre-treatment. Copyright © 2012 Elsevier Ltd. All rights reserved.

US work on technical and economic aspects of electrolytic, thermochemical, and hybrid processes for hydrogen production at temperatures below 550 deg. C

International Nuclear Information System (INIS)

Petri, M.C.; Yyldyz, B.; Klickman, A.E.

2006-01-01

Hydrogen demand is increasing, but there are few options for affordable hydrogen production free of greenhouse gas emissions. Nuclear power is one of the most promising options. Most research is focused on high-temperature electrolytic and thermochemical processes for nuclear-generated hydrogen, but it will be many years before very high temperature reactors become commercially available. For light water reactors or supercritical reactors, low-temperature water electrolysis is a currently available technology for hydrogen production. Higher efficiencies may be gained through thermo-electrochemical hydrogen production cycles, but there are only a limited number that have heat requirements consistent with the lower temperatures of light-water reactor technology. Indeed, active research is ongoing for only three such cycles in the USA. Reductions in electricity and system costs would be needed (or the imposition of a carbon tax) for low-temperature water electrolysis to compete with today's costs for steam methane reformation. The interactions between hydrogen and electricity markets and hydrogen and electricity producers are complex and will evolve as the markets evolve. (author)

Thermochemical hydrogen production studies at LLNL: a status report

International Nuclear Information System (INIS)

Krikorian, O.H.

1982-01-01

Currently, studies are underway at the Lawrence Livermore National Laboratory (LLNL) on thermochemical hydrogen production based on magnetic fusion energy (MFE) and solar central receivers as heat sources. These areas of study were described earlier at the previous IEA Annex I Hydrogen Workshop (Juelich, West Germany, September 23-25, 1981), and a brief update will be given here. Some basic research has also been underway at LLNL on the electrolysis of water from fused phosphate salts, but there are no current results in that area, and the work is being terminated

Secondary reactions of tar during thermochemical biomass conversion[Dissertation 14341

Energy Technology Data Exchange (ETDEWEB)

Morf, P.O.

2001-07-01

This dissertation submitted to the Swiss Federal Institute of Technology in Zurich presents and discusses the results obtained during the examination of the processes involved in the formation and conversion of tar in biomass gasification plant. Details are given on the laboratory reactor system used to provide separated tar production and conversion for the purposes of the experiments carried out. The results of analyses made of the tar and the gaseous products obtained after its conversion at various temperatures are presented. The development of kinetic models using the results of the experiments that were carried out is described. The results of the experiments and modelling are compared with the corresponding results obtained using a full-scale down-draft, fixed-bed gasifier. The author is of the opinion that the reaction conditions found in full-scale gasifiers can be well simulated using heterogeneous tar conversion experiments using the lab reactor system.

Shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Final report

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B.

1998-02-01

Shock heating t-butyl hydroperoxide behind a reflected shock wave has proved to be as a convenient source of hydroxyl radicals at temperatures near 1000 K. We applied this technique to the measurement of reaction rate coefficients of OH with several species of interest in combustion chemistry, and developed a thermochemical kinetics/transition state theory (TK-TST) model for predicting the temperature dependence of OH rate coefficients.

Thermo-chemical production of hydrogen from water by metal oxides fixed on ceramic substrates

International Nuclear Information System (INIS)

Roeb, M.; Monnerie, N.; Schmitz, M.; Sattler, C.; Konstandopoulos, A.G.; Agrafiotis, C.; Zaspalis, V.T.; Nalbandian, L.; Steele, A.; Stobbe, P.

2006-01-01

In the European project HYDROSOL a simple two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split water molecules by abstracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source one has a promising method in hand to produce hydrogen without any environmentally critical emissions. The basic idea is to combine a support capable of achieving high temperatures when heated by concentrated solar radiation, with a redox pair system suitable for water dissociation and at the same time for regeneration at these temperatures, so that complete operation of the whole process could be achieved by a single solar energy converter. The feasibility of the process has proven possible in a mini-plant scale using concentrated sunlight provided by the solar furnace in Cologne. Suitable redox materials as coatings and a dedicated receiver-reactor have been developed to produce hydrogen with significant conversions by repeating several subsequent water splitting and regeneration steps. In a design study a possible way of operating the process in commercial scale is demonstrated. (authors)

Systematic validation of non-equilibrium thermochemical models using Bayesian inference

KAUST Repository

Miki, Kenji

2015-10-01

© 2015 Elsevier Inc. The validation process proposed by Babuška et al. [1] is applied to thermochemical models describing post-shock flow conditions. In this validation approach, experimental data is involved only in the calibration of the models, and the decision process is based on quantities of interest (QoIs) predicted on scenarios that are not necessarily amenable experimentally. Moreover, uncertainties present in the experimental data, as well as those resulting from an incomplete physical model description, are propagated to the QoIs. We investigate four commonly used thermochemical models: a one-temperature model (which assumes thermal equilibrium among all inner modes), and two-temperature models developed by Macheret et al. [2], Marrone and Treanor [3], and Park [4]. Up to 16 uncertain parameters are estimated using Bayesian updating based on the latest absolute volumetric radiance data collected at the Electric Arc Shock Tube (EAST) installed inside the NASA Ames Research Center. Following the solution of the inverse problems, the forward problems are solved in order to predict the radiative heat flux, QoI, and examine the validity of these models. Our results show that all four models are invalid, but for different reasons: the one-temperature model simply fails to reproduce the data while the two-temperature models exhibit unacceptably large uncertainties in the QoI predictions.

Experimental investigation and thermochemical assessment of the system Cu-Y-O

International Nuclear Information System (INIS)

Zimmermann, E.; Mohammad, A.; Boudene, A.; Neuschuetz, D.

1995-01-01

Experimental investigations of the thermochemical properties of the phases in the system Cu-Y-O by means of DTA, EMF, TG and calorimetric measurements are reported. The results together with critically selected data from the literature are used for a complete assessment of the Gibbs energies of the ternary phases (based on the Standard Element Reference State, SER). For the binary subsystems critically assessed data from the literature are used. (orig.)

Experimental Investigation of the ^{19}Ne(p,γ)^{20}Na Reaction Rate and Implications for Breakout from the Hot CNO Cycle.

Science.gov (United States)

Belarge, J; Kuvin, S A; Baby, L T; Baker, J; Wiedenhöver, I; Höflich, P; Volya, A; Blackmon, J C; Deibel, C M; Gardiner, H E; Lai, J; Linhardt, L E; Macon, K T; Need, E; Rasco, B C; Quails, N; Colbert, K; Gay, D L; Keeley, N

2016-10-28

The ^{19}Ne(p,γ)^{20}Na reaction is the second step of a reaction chain which breaks out from the hot CNO cycle, following the ^{15}O(α,γ)^{19}Ne reaction at the onset of x-ray burst events. We investigate the spectrum of the lowest proton-unbound states in ^{20}Na in an effort to resolve contradictions in spin-parity assignments and extract reliable information about the thermal reaction rate. The proton-transfer reaction ^{19}Ne(d,n)^{20}Na is measured with a beam of the radioactive isotope ^{19}Ne at an energy around the Coulomb barrier and in inverse kinematics. We observe three proton resonances with the ^{19}Ne ground state, at 0.44, 0.66, and 0.82 MeV c.m. energies, which are assigned 3^{+}, 1^{+}, and (0^{+}), respectively. In addition, we identify two resonances with the first excited state in ^{19}Ne, one at 0.20 MeV and one, tentatively, at 0.54 MeV. These observations allow us for the first time to experimentally quantify the astrophysical reaction rate on an excited nuclear state. Our experiment shows an efficient path for thermal proton capture in ^{19}Ne(p,γ)^{20}Na, which proceeds through ground state and excited-state capture in almost equal parts and eliminates the possibility for this reaction to create a bottleneck in the breakout from the hot CNO cycle.

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

Science.gov (United States)

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.

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

Science.gov (United States)

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

2016-06-13

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.

Thermochemical properties of some alkaline-earth silicates and zirconates. Fission product behaviour during molten core-concrete interactions

International Nuclear Information System (INIS)

Huntelaar, M.E.

1996-01-01

This thesis aims to make a contribution to a better understanding of the chemical processes occurring during an ex-vessel MCCI accident with a western-type of nuclear reactor. Chosen is for a detailed thermochemical study of the silicates and zirconates of barium and strontium. In Chapter one a short introduction in the history of (research in) nuclear safety is given, followed by the state-of-the-art of molten core-concrete interactions in Chapter two. In both Chapters the role of chemical thermodynamics on this particular subject is dealt with. The experimental work on the silicates and zirconates of barium and strontium performed for this thesis, is described in the Chapters three, four, five, six, and parts of eight. In Chapter three the basis for all thermochemical measurements, the sample preparation is given. Because the sample preparation effects the accuracy of the thermodynamic measurements, a great deal of effort is spent in optimizing the synthesis of the silicates which resulted in the TEOS-method widely employed here. In the next Chapters the different thermochemical techniques used, are described: The low-temperature heat capacity measurements and the enthalpy increment measurements in Chapter four, the enthalpy-of-solution measurements in Chapter five, and measurements to determine the crystal structures in Chapter six. (orig.)

Thermochemical properties of some alkaline-earth silicates and zirconates. Fission product behaviour during molten core-concrete interactions

Energy Technology Data Exchange (ETDEWEB)

Huntelaar, M.E.

1996-06-19

This thesis aims to make a contribution to a better understanding of the chemical processes occurring during an ex-vessel MCCI accident with a western-type of nuclear reactor. Chosen is for a detailed thermochemical study of the silicates and zirconates of barium and strontium. In Chapter one a short introduction in the history of (research in) nuclear safety is given, followed by the state-of-the-art of molten core-concrete interactions in Chapter two. In both Chapters the role of chemical thermodynamics on this particular subject is dealt with. The experimental work on the silicates and zirconates of barium and strontium performed for this thesis, is described in the Chapters three, four, five, six, and parts of eight. In Chapter three the basis for all thermochemical measurements, the sample preparation is given. Because the sample preparation effects the accuracy of the thermodynamic measurements, a great deal of effort is spent in optimizing the synthesis of the silicates which resulted in the TEOS-method widely employed here. In the next Chapters the different thermochemical techniques used, are described: The low-temperature heat capacity measurements and the enthalpy increment measurements in Chapter four, the enthalpy-of-solution measurements in Chapter five, and measurements to determine the crystal structures in Chapter six. (orig.).

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

Science.gov (United States)

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.

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Zaitsau, Dzmitry H.; Emeĺyanenko, Vladimir N.; Stepurko, Elena N.; Zherikova, Kseniya V.

2015-01-01

Highlights: • Vapor pressures of benzoic acid derivatives were measured. • Sublimation enthalpies were derived and compared with the literature. • Thermochemical data tested for consistency using additivity rules and computations. • Contradiction between available enthalpies of sublimation was resolved. • Pairwise interactions of substituents on the benzene ring were derived. - Abstract: Molar sublimation enthalpies of the methyl- and methoxybenzoic acids were derived from the transpiration method, static method, and TGA. Thermochemical data available in the literature were collected, evaluated, and combined with own experimental results. This collection together with the new experimental results reported here has helped to resolve contradictions in the available enthalpy data and to recommend sets of sublimation and formation enthalpies for the benzoic acid derivatives. Gas-phase enthalpies of formation calculated with the G4 quantum-chemical method were in agreement with the experiment. Pairwise interactions of the methyl, methoxy, and carboxyl substituents on the benzene ring were derived and used for the development of simple group-additivity procedures for estimation of the vaporization enthalpies, gas-phase, and liquid-phase enthalpies of formation of substituted benzenes.

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

Energy Technology Data Exchange (ETDEWEB)

Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry and Department “Science and Technology of Life, Light and Matter”, University of Rostock, D-18059 Rostock (Germany); Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Zaitsau, Dzmitry H. [Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Emeĺyanenko, Vladimir N. [Department of Physical Chemistry and Department “Science and Technology of Life, Light and Matter”, University of Rostock, D-18059 Rostock (Germany); Stepurko, Elena N. [Chemistry Faculty and Research Institute for Physical Chemical Problems, Belarusian State University, 220030 Minsk (Belarus); Zherikova, Kseniya V. [Nikolaev Institute of Inorganic Chemistry of Siberian Branch of Russian Academy of Sciences, 630090 Novosibirsk (Russian Federation)

2015-12-20

Highlights: • Vapor pressures of benzoic acid derivatives were measured. • Sublimation enthalpies were derived and compared with the literature. • Thermochemical data tested for consistency using additivity rules and computations. • Contradiction between available enthalpies of sublimation was resolved. • Pairwise interactions of substituents on the benzene ring were derived. - Abstract: Molar sublimation enthalpies of the methyl- and methoxybenzoic acids were derived from the transpiration method, static method, and TGA. Thermochemical data available in the literature were collected, evaluated, and combined with own experimental results. This collection together with the new experimental results reported here has helped to resolve contradictions in the available enthalpy data and to recommend sets of sublimation and formation enthalpies for the benzoic acid derivatives. Gas-phase enthalpies of formation calculated with the G4 quantum-chemical method were in agreement with the experiment. Pairwise interactions of the methyl, methoxy, and carboxyl substituents on the benzene ring were derived and used for the development of simple group-additivity procedures for estimation of the vaporization enthalpies, gas-phase, and liquid-phase enthalpies of formation of substituted benzenes.

Radioisotope methods of investigations of phenomenons at phases border of steel - atmosphere in gaseous processes of thermochemical treatment of steel

International Nuclear Information System (INIS)

L'utse-Birk, A.; Bel'ski, V.; Vez'ranovski, Eh.; Valis', L.

1979-01-01

Radioisotope methods of investigations of the processes of thermochemical treatment of steels are valuable, and in some cases, the only means for analysis of complicated mechanisms of diffusion, absorption and chemical reactions, going on in some technological processes. New specific methods are stated for investigation of processes on the border between steel and gaseous atmosphere. Quantative method nas been developed for investigation of the kinetics of carbon transfere (labelled by carbon-14) from steel into gases. Hydrocarbons and their derivatives are adsorbed selectivelly and beta-activity of the compound is measured in the presence of liquid scintillators. Limiting detectable amount of carbon equals to 0.5μg. Application of labelled (by radioisotope iron-59) iron in steel has ensured a possibility to determine its participation in reactions with chromium and titanum coating atmospheres. Application of hydrocarbons labelled by carbon-14 in the composition of titanum coating atmosphere has permitted to determine, in comparison with investigation of carbon diffusion in steel, participation of two different carbon sources in the forming of the TiC layer on steel and has led to the optimization of processes, especially for low-carbon steels [ru

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

Science.gov (United States)

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

Wuestite - a solar energy carrier

Energy Technology Data Exchange (ETDEWEB)

Weidenkaff, A; Nueesch, P; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Reller, A [Hamburg Univ., Hamburg (Germany)

1997-06-01

Hydrogen is produced when Wuestite (Fe{sub 1-y}O) is oxidised by water. This reaction is part of a two-step thermochemical metal oxide cycle for the storage of solar energy in the form of chemical energy carriers, characterised by a high chemical potential. The reaction was studied in a tubular furnace with on-line gas analysis and further characterised in detail by DTA und high-temperature X-ray powder diffraction. The influence of non-stoichiometry, morphology and temperature on the mechanism and kinetics of the water-splitting reaction was determined. (author) 3 figs., tabs., 3 refs.

Clean energy and hydrogen for oil sands development with CANDU SCWR nuclear reactors and Cu-Cl cycles

International Nuclear Information System (INIS)

Wang, Z.L.; Naterer, G.F.; Gabriel, K.S.

2010-01-01

In this paper, the unique capabilities and advantages of SCWR technology for cleaner oil sands development are discussed from two perspectives: lower temperature steam generation by supercritical water for steam assisted gravity drainage (SAGD), and hydrogen production for oil sands upgrading by coupling SCWR with the thermochemical copper-chlorine (Cu-Cl) cycle. The heat requirements for bitumen extraction from the oil sands and the hydrogen requirements for bitumen upgrading are evaluated. A conceptual layout of SCWR coupled with oil sands development is presented. The reduction of CO 2 emissions due to the use of SCWR and thermo chemical hydrogen production cycle is also analyzed. (author)

H2-assisted CO2 thermochemical reduction on La0.9Ca0.1FeO3-δ membranes: a kinetics study

KAUST Repository

Wu, Xiao-Yu; Ghoniem, Ahmed F.

2017-01-01

Kinetics data for CO2 thermochemical reduction in an isothermal membrane reactor is required to identify the rate-limiting steps. Here, we report a detailed reaction kinetics study on this process supported by an La0.9Ca0.1FeO3-δ (LCF-91) membrane. The dependence of CO2 reduction rate on various operating conditions is examined such as CO2 concentration on the feed side, fuel concentrations on the sweep side and temperatures. CO2 reduction rate is proportional to the oxygen flux across the membrane, and the measured maximum fluxes are 0.191 and 0.164 μmol cm-2 s-1 with 9.5% H2 and 11.6% CO on the sweep side at 990oC, respectively. Fuel is used to maintain the chemical potential gradient across the membrane and CO is used by construction to derive the surface reaction kinetics. This membrane also exhibits stable performances for 106 hours. A resistance-network model is developed to describe the oxygen transport process and the kinetics data are parameterized using the experimental values. The model shows a transition of the rate limiting step between the surface reactions on the feed side and the sweep side depending on the operating conditions.

H2-assisted CO2 thermochemical reduction on La0.9Ca0.1FeO3-δ membranes: a kinetics study

KAUST Repository

Wu, Xiao-Yu

2017-11-04

Kinetics data for CO2 thermochemical reduction in an isothermal membrane reactor is required to identify the rate-limiting steps. Here, we report a detailed reaction kinetics study on this process supported by an La0.9Ca0.1FeO3-δ (LCF-91) membrane. The dependence of CO2 reduction rate on various operating conditions is examined such as CO2 concentration on the feed side, fuel concentrations on the sweep side and temperatures. CO2 reduction rate is proportional to the oxygen flux across the membrane, and the measured maximum fluxes are 0.191 and 0.164 μmol cm-2 s-1 with 9.5% H2 and 11.6% CO on the sweep side at 990oC, respectively. Fuel is used to maintain the chemical potential gradient across the membrane and CO is used by construction to derive the surface reaction kinetics. This membrane also exhibits stable performances for 106 hours. A resistance-network model is developed to describe the oxygen transport process and the kinetics data are parameterized using the experimental values. The model shows a transition of the rate limiting step between the surface reactions on the feed side and the sweep side depending on the operating conditions.

Evaluation and Characterization of Membranes for HI/H2O/I2 Water Separation for the S-I Cycle

Energy Technology Data Exchange (ETDEWEB)

Frederick F. Stewart

2005-09-01

In the Sulfur-Iodine (S-I) thermochemical cycle, iodine is added to the product of the Bunsen reaction to facilitate the separation of sulfuric acid (H2SO4) from hydriodic acid (HI). The amount of iodine can be as high as 83% of the overall mass load of the Bunsen product stream, which potentially introduces a large burden on the cycle’s efficiency. Removal of water from the HI and I2 mixture would substantially reduce the amount of required additional iodine. In this work, Nafion® membranes have been studied for their use as de-watering membranes. Specifically, two thicknesses of Nafion membranes have been found to be effective in this application. The thicker membrane, Nafion-117®, produces moderate fluxes of water with very high separation factors. On the other hand, the thinner membrane, Nafion-112®, yielded very large fluxes of water, however with smaller separation factors. All membranes were found to be durable and did not degrade in contact with the feed stream over periods of time up to three months.

FY 1985 report on research and development project commissioned by the Sunshine Project. Research and development of electrolysis of water by combined thermochemical, photochemical and electrochemical cycles; 1985 nendo netsu kagaku, hikari kagaku, denki kagaku konsei cycle ni yoru mizu bunkai no kenkyu kaihatsu seika hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1986-03-01

Reported herein are the FY 1985 research results on the combined water electrolysis cycles by effective utilization of sunlight. The tests for determining activity coefficient of an iron/iodine system is continued from the previous year, and the results are used to find the optimum conditions under which the photochemical and electrolysis reactions are effected simultaneously in a light-irradiated electrolysis tank. It is found that a photochemical reaction efficiency of approximately 0.3% is obtained at 5 W/cm{sup 2} as light intensity and 25 degrees C. For electrolysis of water by the multi-stage hybrid cycles, it is necessary for the reaction in each stage to proceed to almost the same extent so that it gives a just enough quantity of product for the subsequent stage. The data obtained are analyzed comprehensively, while taking the system matching conditions into consideration. The system for simultaneously measure two or more parameters, developed in the previous year, is equipped with a high-level language compiler of high effective speed, to simultaneously measure these parameters at shorter intervals. (NEDO)

The kinetics of the photochemical reaction cycle of deuterated bacteriorhodopsin and pharaonis halorhodopsin

International Nuclear Information System (INIS)

Szakacs, Julianna; Lakatos, Melinda; Varo, Gy.; Ganea, Constanta

2005-01-01

Kinetic isotope effects in the photochemical reaction cycle of bacteriorhodopsin and pharaonis halorhodopsin were determined in H 2 O and D 2 O at normal pH, to get insight in the proton dependent steps of the transport process. All the steps of the bacteriorhodopsin photocycle at normal pH exhibited a strong isotope effect. In the case of halorhodopsin in both the chloride and nitrate transporting conditions the photocycle was not strongly affected by the deuterium exchange. In the case of chloride, a slight slow down of the photocycle could be observed. On the opposite, in the nitrate transport conditions a reverse effect is present. (author)

The influence of menstrual cycle and androstadienone on female stress reactions: an fMRI study.

Directory of Open Access Journals (Sweden)

Ka Chun eChung

2016-02-01

Full Text Available Communicating threats and stress via biological signaling is common in animals. In humans, androstadienone (ANDR, a synthetic male steroid, is a socially relevant chemosignal exhibited to increase positive mood and cortisol levels specifically in (periovulatory females in positively arousing contexts. In a negative context, we expected that such effects of ANDR could amplify social evaluative threat depending on the stress sensitivity, which differs between menstrual cycle phases. Therefore, this fMRI study aimed to examine psychosocial stress reactions on behavioral, hormonal and neural levels in 31 naturally cycling females, between 15 early follicular (EF and 16 mid-luteal (ML females tested with ANDR and placebo treatment in a repeated-measures design.Regardless of odor stimulation, psychosocial stress (i.e. mental arithmetic task with social evaluative threat led to elevated negative mood and anxiety in all females. A negative association of social threat related amygdala activation and competence ratings appeared in ML-females, indicating enhanced threat processing by ANDR, particularly in ML-females who felt less competent early in the stress experience. Further, ML-females showed reduced performance and stronger stress-related hippocampus activation compared to EF-females under ANDR. Hippocampal activation in ML-females also correlated positively with post-stress subjective stress. Contrarily, such patterns were not observed in EF-females or under placebo in either group. Strikingly, unlike passive emotional processing, ANDR in a stressful context decreased cortisol concentration in all females. This points to a more complex interaction of ovarian/gonadal hormones in social threat processing and stress reactivity.Our findings suggest that ANDR enhanced initial evaluation of self-related social threat in ML-females. Female stress reactions are related to stress sensitivity through enhanced awareness and processing of social cues in a

Nicotinamides: Evaluation of thermochemical experimental properties

International Nuclear Information System (INIS)

Zhabina, Aleksandra A.; Nagrimanov, Ruslan N.; Emel’yanenko, Vladimir N.; Solomonov, Boris N.; Verevkin, Sergey P.

2016-01-01

Highlights: • Vapor pressures measured by transpiration method. • Enthalpies of solution measured using high-precision solution calorimetry. • Enthalpies of fusion measured by DSC. • Sublimation enthalpies derived from transpiration and solution calorimetry in agreement. • Experimental results evaluated and compared with G4 calculations. - Abstract: Vapor pressures of the isomeric 2-, 3-, and 4-pyridinecarboxamides were measured by using the transpiration method. The enthalpies of sublimation/vaporization of these compounds at 298.15 K were derived from vapor pressure temperature dependences. The enthalpies of solution of the isomeric pyridinecarboxamides were measured with the high-precision solution calorimetry. The enthalpies of sublimation of 3- and 4-pyridinecarboxamides were independently derived with help of the solution calorimetry based procedure. The enthalpies of fusion of the pyridinecarboxamides were measured by the DSC. Thermochemical data isomeric pyridinecarboxamides were collected, evaluated, and tested for internal consistency. The high-level G4 quantum-chemical method was used for mutual validation of the experimental and theoretical gas phase enthalpies of formation successfully.

Achievement report for 1st phase (fiscal 1974-80) Sunshine Program research and development - Hydrogen energy. Research on hydrogen production technology using thermochemical method (Research on iodine-based cycle etc.); 1974-1980 nendo netsukagakuho ni yoru suiso seizo gijutsu no kenkyu seika hokokusho. Yosokei cycle nado no kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1981-03-01

Iodine-alkaline earth metal (Mg, Ca) cycles are discovered, and the one with Mg is found excellent. The reaction consists of four stages, that is, Stage (1) where 1/5Mg(IO{sub 3}){sub 2}+MgI{sub 2}(aq) is obtained from 6/5MgO+6/5I{sub 2}, Stage (2) where 1/5MgO+1/5I{sub 2}+1/2O{sub 2} is obtained from 1/5Mg(IO{sub 3}){sub 2}, Stage (3) where MgO+2HI is obtained from MgI{sub 2}+H{sub 2}O, and Stage (4) where H{sub 2}+I{sub 2} is obtained from 2HI. Since there is much iodine and water at Stage (1), MgO thrice MgI{sub 2} in mol is added for reforming and concentration. At Stage (4), where the decomposition rate is as low as 17-27% with the equilibrium dissociation reaction proceeding at 300-700 degrees C, hydrogen is selectively separated by permeation through a porous diaphragm for the acceleration of the reaction. As for materials for the device, they are narrowed down to high-priced ones, that is, Ta and Nb for Stage (1), Ni-50Cr for Stage (2), and Mo etc. for Stages (3) and (4). Under the circumstances, a study is started for the development of a chemical vapor plating process which is high in corrosion resistance. Other cycles such as sulfur-based cycles and hybrid cycles are also investigated. (NEDO)

Thermodynamic analysis of chemical heat pumps

International Nuclear Information System (INIS)

Obermeier, Jonas; Müller, Karsten; Arlt, Wolfgang

2015-01-01

Thermal energy storages and heat pump units represent an important part of high efficient renewable energy systems. By using thermally driven, reversible chemical reactions a combination of thermal energy storage and heat pump can be realized. The influences of thermophysical properties of the involved components on the efficiency of a heat pump cycle is analysed and the relevance of the thermodynamic driving force is worked out. In general, the behaviour of energetic and exergetic efficiency is contrary. In a real cycle, higher enthalpies of reaction decrease the energetic efficiency but increase the exergetic efficiency. Higher enthalpies of reaction allow for lower offsets from equilibrium state for a default thermodynamic driving force of the reaction. - Highlights: • A comprehensive efficiency analysis of gas-solid heat pumps is proposed. • Link between thermodynamic driving force and equilibrium drop is shown. • Calculation of the equilibrium drop based on thermochemical properties. • Reaction equilibria of the decomposition reaction of salt hydrates. • Contrary behavior of energetic and exergetic efficiency

Thermochemical micro imprinting of single-crystal diamond surface using a nickel mold under high-pressure conditions

Energy Technology Data Exchange (ETDEWEB)

Imoto, Yuji; Yan, Jiwang, E-mail: yan@mech.keio.ac.jp

2017-05-15

Graphical abstract: A Ni mold and thermochemically imprinted microstructures on diamond. - Highlights: • A thermochemical method for micro machining/patterning of diamond is proposed. • Various kinds of microstructures were imprinted on diamond using a Ni mold. • A graphite layer is formed during imprinting which can be removed by acid. • The processing depth depends strongly on pressure and temperature. - Abstract: Single-crystal diamond is an important material for cutting tools, micro electro mechanical systems, optical devices, and semiconductor substrates. However, the techniques for producing microstructures on diamond surface with high efficiency and accuracy have not been established. This paper proposes a thermochemical imprinting method for transferring microstructures from a nickel (Ni) mold onto single-crystal diamond surface. The Ni mold was micro-structured by a nanoindenter and then pressed against the diamond surface under high temperature and pressure in argon atmosphere. Results show that microstructures on the Ni mold were successfully transferred onto the diamond surface, and their depth increased with both pressure and temperature. Laser micro-Raman spectroscopy, transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) analyses indicate that a graphite layer was formed over the contact area between diamond and Ni during pressing, and after washing by a mixed acid, the graphite layer could be completely removed. This study demonstrated the feasibility of a cost-efficient fabrication method for large-area microstructures on single-crystal diamond.

Nagra thermochemical data base. II. Supplement data 05/92

International Nuclear Information System (INIS)

Pearson, F.J.; Berner, U.; Hummel, W.

1992-05-01

Chemical thermodynamic data for aqueous species, minerals, and gases are required by Nagra for geochemical modelling. The Nagra thermochemical data base contains core and supplemental data. Core data for well-characterised entities were individually carefully selected and given by Pearson and Berner (1991). Supplemental data are for less common entities and for elements principally of safety assessment concern. They were selected in groups from other data bases for geochemical modelling and did not receive individual scrutiny. This report gives tables with the Nagra thermochemical data as of 5/92. It includes the core data described in the earlier report with supplemental data for the elements aluminium, silicon, iron, and manganese, the actinides thorium, uranium, neptunium, plutonium, and americium, and elements found as fission or activation products in nuclear waste, including nickel, zirconium, niobium, molybdenum, technetium, palladium, tin, selenium and iodine. Aqueous complexes of four representative organic anions are also included. The sources of these supplemental data are described in the text. Other compilations of data were examined during the selection on the supplemental data. These included the data bases used at the Paul Scherrer Institut with the geochemical programs MINEQL as of 3/91, PHREEQE as of 4/91, and the HATCHES 3.0 data base. This report also gives tables comparing selected data in these three data bases with values from the Nagra data base. This data base has not yet been tested for a full range of nuclear waste management applications, although such work is in progress. It should thus be regarded as a reference fixed point for quality assurance purpose and not critically reviewed standard. (author) tabs., refs

Analysis and optimal process development of the iodine-Sulfur cycle for nuclear hydrogen production

International Nuclear Information System (INIS)

Lee, Byung Jin

2009-02-01

Hydrogen is expected to be a main energy vector for the future society. Among many thermo-chemical water splitting technologies for mass production of hydrogen, Iodine-Sulfur (I-S) cycle is considered to be the most promising one. Originated in the 1980s by General Atomics in the United States, the I-S cycle utilizes high temperature heat from energy sources such as nuclear reactors. Despite its high viability relative to many other options, lots of technical challenges need to be resolved until it can practically contribute to the mass production of hydrogen. In the present work, based on the experimental data available from previous works and discussions collected through the literature survey, the optimal operating conditions were proposed for the Bunsen reaction, considering the key concerns of the I-S cycle: i.e., the liquid-liquid (L-L) phase separation performance, the water distributions between the sulfuric acid and poly-hydroiodic acid (HI x ) phases, the side reactions, and the operating cost due to the excess iodine and water. All the available experimental data were combined together, and a series of parametric studies were done to find out any trends among parameters. The optimal operating point is determined as 4 mol of excess iodine and 11 mol of excess water in the stoichiometry at temperature of 330K, while the allowable window ranges between 4∼6 mol for excess iodine, 11∼13 moles for excess water, and 330∼350K for temperature. As for the distribution of excess water after the Bunsen reaction and L-L phase separation, 5 mol moves to the sulfuric acid phase and 6∼8 mol to the HI x phase. By controlling the operation within this window, it should be possible to avoid the side reaction and iodine solidification, to increase the HI concentration well above the azeotrope in the HI x section, and to minimize the operating cost caused by the excess iodine and water. With the optimized Bunsen reaction process to yield an over-azeotropic HI liquid

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

Science.gov (United States)

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.

Characteristic of the Pressurized Continuous Bunsen Reaction using HIx Solution

Directory of Open Access Journals (Sweden)

Kim Jong-Seok

2016-01-01

Full Text Available The Sulfur-Iodine thermochemical hydrogen production process (SI process consists of the Bunsen reaction section, the H2SO4 decomposition section and the HI decomposition section. The HIx solution (HI-I2-H2O could be recycled to Bunsen reaction section from the HI decomposition section in the operation of the integrated SI process. The phase separation characteristic of the Bunsen reaction using the HIx solution was similar to that of SO2-I2-H2O system. However, the amount of produced H2SO4 phase was too small. To solve this problem, the study was carried out by the pressurized continuous Bunsen reaction. Bunsen reactions were performed at variation of feed rate of SO2/O2 gas in 3 bar of atmosphere. Also, it was performed to check the effects of the residence time in the reservoir on the characteristics of Bunsen products. As the results, the concentration of H2SO4 and HI in Bunsen products was increased with increasing the amounts of SO2. When the residence time in the reservoir increased, the concentration of H2SO4 and HI in HIx phase was decreased by reverse Bunsen reaction.

Positronium hydride defects in thermochemically reduced alkaline-Earth oxides

International Nuclear Information System (INIS)

Monge, M.A.; Pareja, R.; Gonzalez, R.; Chen, Y.

1997-01-01

Thermochemical reduction of both hydrogen-doped MgO and CaO single crystals results in large concentrations of hydride (H - ) ions. In MgO crystals, positron lifetime and Doppler broadening experiments show that positrons are trapped at H - centers forming positronium hydride molecules [e + - H - ]. A value of 640 ps is obtained for the lifetime of the PsH states located in an anion vacancy In MgO positrons are also trapped at H 2- sites at low temperatures. The H 2- ions were induced in the crystals by blue light illumination. The formation of PsH states in CaO could not be conclusively established. (orig.)

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

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

Science.gov (United States)

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.

Effect of thermal, chemical and thermo-chemical pre-treatments to enhance methane production

Energy Technology Data Exchange (ETDEWEB)

Rafique, Rashad; Nizami, Abdul-Sattar; Murphy, Jerry D.; Kiely, Gerard [Department of Civil and Environmental Engineering, University College Cork (Ireland); Poulsen, Tjalfe Gorm [Department of Biotechnology, Chemistry and Environmental Engineering, Aalborg University (Denmark); Asam, Zaki-ul-Zaman [Department of Civil Engineering, National University of Ireland Galway (Ireland)

2010-12-15

The rise in oil price triggered the exploration and enhancement of various renewable energy sources. Producing biogas from organic waste is not only providing a clean sustainable indigenous fuel to the number of on-farm digesters in Europe, but also reducing the ecological and environmental deterioration. The lignocellulosic substrates are not completely biodegraded in anaerobic digesters operating at commercial scale due to their complex physical and chemical structure, which result in meager energy recovery in terms of methane yield. The focus of this study is to investigate the effect of pre-treatments: thermal, thermo-chemical and chemical pre-treatments on the biogas and methane potential of dewatered pig manure. A laboratory scale batch digester is used for these pre-treatments at different temperature range (25 C-150 C). Results showed that thermo-chemical pretreatment has high effect on biogas and methane potential in the temperature range (25-100 C). Maximum enhancement is observed at 70 C with increase of 78% biogas and 60% methane production. Thermal pretreatment also showed enhancement in the temperature range (50-10 C), with maximum enhancement at 100 C having 28% biogas and 25% methane increase. (author)

Aerobic dive limits of seals with mutant myoglobin using combined thermochemical and physiological data

DEFF Research Database (Denmark)

Dasmeh, Pouria; Davis, Randall W.; Kepp, Kasper Planeta

2013-01-01

This paper presents an integrated model of convective O2-transport, aerobic dive limits (ADL), and thermochemical data for oxygen binding to mutant myoglobin (Mb), used to quantify the impact of mutations in Mb on the dive limits of Weddell seals (Leptonychotes weddellii). We find that wild-type ...... that such conditions are mostly selected upon in seals. The model is capable of roughly quantifying the physiological impact of single-protein mutations and thus bridges an important gap between animal physiology and molecular (protein) evolution.......This paper presents an integrated model of convective O2-transport, aerobic dive limits (ADL), and thermochemical data for oxygen binding to mutant myoglobin (Mb), used to quantify the impact of mutations in Mb on the dive limits of Weddell seals (Leptonychotes weddellii). We find that wild-type Mb...... traits are only superior under specific behavioral and physiological conditions that critically prolong the ADL, action radius, and fitness of the seals. As an extreme example, the mutations in the conserved His-64 reduce ADL up to 14±2 min for routine aerobic dives, whereas many other mutations...

Consistent post-reaction vibrational energy redistribution in DSMC simulations using TCE model

Science.gov (United States)

Borges Sebastião, Israel; Alexeenko, Alina

2016-10-01

The direct simulation Monte Carlo (DSMC) method has been widely applied to study shockwaves, hypersonic reentry flows, and other nonequilibrium flow phenomena. Although there is currently active research on high-fidelity models based on ab initio data, the total collision energy (TCE) and Larsen-Borgnakke (LB) models remain the most often used chemistry and relaxation models in DSMC simulations, respectively. The conventional implementation of the discrete LB model, however, may not satisfy detailed balance when recombination and exchange reactions play an important role in the flow energy balance. This issue can become even more critical in reacting mixtures involving polyatomic molecules, such as in combustion. In this work, this important shortcoming is addressed and an empirical approach to consistently specify the post-reaction vibrational states close to thermochemical equilibrium conditions is proposed within the TCE framework. Following Bird's quantum-kinetic (QK) methodology for populating post-reaction states, the new TCE-based approach involves two main steps. The state-specific TCE reaction probabilities for a forward reaction are first pre-computed from equilibrium 0-D simulations. These probabilities are then employed to populate the post-reaction vibrational states of the corresponding reverse reaction. The new approach is illustrated by application to exchange and recombination reactions relevant to H2-O2 combustion processes.

Definitive Ideal-Gas Thermochemical Functions of the (H2O)-O-16 Molecule

Czech Academy of Sciences Publication Activity Database

Furtenbacher, T.; Szidarovszky, T.; Hrubý, Jan; Kyuberis, A. A.; Zobov, N. F.; Polyansky, O. L.; Tennyson, J.; Császár, A. G.

2016-01-01

Roč. 45, č. 4 (2016), č. článku 043104. ISSN 0047-2689 R&D Projects: GA ČR(CZ) GA16-02647S Institutional support: RVO:61388998 Keywords : ideal-gas thermochemical quantities * ortho- and para-H2 16O * partition function Subject RIV: BJ - Thermodynamics Impact factor: 4.204, year: 2016 http://aip.scitation.org/doi/pdf/10.1063/1.4967723

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

Science.gov (United States)

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%.

Sensitivity study on nitrogen Brayton cycle coupled with a small ultra-long cycle fast reactor

International Nuclear Information System (INIS)

Seo, Seok Bin; Seo, Han; Bang, In Cheol

2014-01-01

The main characteristics of UCFR are constant neutron flux and power density. They move their positions every moment at constant speed along with axial position of fuel rod for 60 years. Simultaneously with the development of the reactors, a new power conversion system has been considered. To solve existing issues of vigorous sodium-water reaction in SFR with steam power cycle, many researchers suggested a closed Brayton cycle as an alternative technique for SFR power conversion system. Many inactive gases are selected as a working fluid in Brayton power cycle, mainly supercritical CO 2 (S-CO 2 ). However, S-CO 2 still has potential for reaction with sodium. CO 2 -sodium reaction produces solid product, which has possibility to have an auto ignition reaction around 600 .deg. C. Thus, instead of S-CO 2 , CEA in France has developed nitrogen power cycle for ASTRID (Advanced Sodium Technological Reactor for Industrial Demonstration). In addition to inactive characteristic of nitrogen with sodium, its thermal and physical similarity with air enables to easily adopt to existing air Brayton cycle technology. In this study, for an optimized power conversion system for UCFR, a nitrogen Brayton cycle was analyzed in thermodynamic aspect. Based on subchannel analysis data of UCFR-100, a parametric study for thermal performance of nitrogen Brayton cycle was achieved. The system maximum pressure significantly affects to the overall efficiency of cycle, while other parameters show little effects. Little differences of the overall efficiencies for all cases between three stages (BOC, MOC, EOC) indicate that the power cycle of UCFR-100 maintains its performance during the operation

Comparison of second-generation processes for the conversion of sugarcane bagasse to liquid biofuels in terms of energy efficiency, pinch point analysis and Life Cycle Analysis

International Nuclear Information System (INIS)

Petersen, A.M.; Melamu, Rethabi; Knoetze, J.H.; Görgens, J.F.

2015-01-01

Highlights: • Process evaluation of thermochemical and biological routes for bagasse to fuels. • Pinch point analysis increases overall efficiencies by reducing utility consumption. • Advanced biological route increased efficiency and local environmental impacts. • Thermochemical routes have the highest efficiencies and low life cycle impacts. - Abstract: Three alternative processes for the production of liquid transportation biofuels from sugar cane bagasse were compared, on the perspective of energy efficiencies using process modelling, Process Environmental Assessments and Life Cycle Assessment. Bio-ethanol via two biological processes was considered, i.e. Separate Hydrolysis and Fermentation (Process 1) and Simultaneous Saccharification and Fermentation (Process 2), in comparison to Gasification and Fischer Tropsch synthesis for the production of synthetic fuels (Process 3). The energy efficiency of each process scenario was maximised by pinch point analysis for heat integration. The more advanced bio-ethanol process was Process 2 and it had a higher energy efficiency at 42.3%. Heat integration was critical for the Process 3, whereby the energy efficiency was increased from 51.6% to 55.7%. For both the Process Environmental and Life Cycle Assessment, Process 3 had the least potential for detrimental environmental impacts, due to its relatively high energy efficiency. Process 2 had the greatest Process Environmental Impact due to the intensive use of processing chemicals. Regarding the Life Cycle Assessments, Process 1 was the most severe due to its low energy efficiency

Development program of hydrogen production by thermo-chemical water splitting is process

International Nuclear Information System (INIS)

Ryutaro Hino

2005-01-01

The Japan Atomic Energy Research Institute (JAERI) has been conducting R and D on the HTGR and also on thermo-chemical water splitting hydrogen production by using a iodine-sulfur cycle (IS process) in the HTTR project. The continuous hydrogen production for one week was demonstrated with a bench-scale test apparatus made of glass, and the hydrogen production rare was about 31 NL/h. Based on the test results and know-how obtained through the bench-scale test, a pilot test plant, which has a hydrogen production performance of 30 Nm 3 /h and will be operated under the high pressure up to 2 MPa, is being designed conceptually as the next step of the IS process development aiming to realize a future nuclear hydrogen production coupled with the HTGR. In this paper, we will introduce one-week continuous hydrogen production conducted with the bench-scale test apparatus and the pilot test program including R and D and an analytical system necessary for designing the pilot test plant. MW. Figure 1 shows an overview of the HTTR-IS plant. In this paper, we will introduce latest test results obtained with the bench-scale test apparatus and concepts of key components of the IS process, a sulfuric acid (H 2 SO 4 ) and a sulfur trioxide (SO 3 ) decomposers working under high-temperature corrosive circumstance, are also introduced as well as relating R and D and an analytical system for the pilot plant design. (authors)

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

Science.gov (United States)

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.

Efficiency of two-step solar thermochemical non-stoichiometric redox cycles with heat recovery

International Nuclear Information System (INIS)

Lapp, J.; Davidson, J.H.; Lipiński, W.

2012-01-01

Improvements in the effectiveness of solid phase heat recovery and in the thermodynamic properties of metal oxides are the most important paths to achieving unprecedented thermal efficiencies of 10% and higher in non-stoichiometric solar redox reactors. In this paper, the impact of solid and gas phase heat recovery on the efficiency of a non-stoichiometric cerium dioxide-based H 2 O/CO 2 splitting cycle realized in a solar-driven reactor are evaluated in a parametric thermodynamic analysis. Application of solid phase heat recovery to the cycling metal oxide allows for lower reduction zone operating temperatures, simplifying reactor design. An optimum temperature for metal oxide reduction results from two competing phenomena as the reduction temperature is increased: increasing re-radiation losses from the reactor aperture and decreasing heat loss due to imperfect solid phase heat recovery. Additionally, solid phase heat recovery increases the efficiency gains made possible by gas phase heat recovery. -- Highlights: ► Both solid and gas phase heat recovery are essential to achieve high thermal efficiency in non-stoichiometric ceria-based solar redox reactors. ► Solid phase heat recovery allows for lower reduction temperatures and increases the gains made possible by gas phase heat recovery. ► The optimum reduction temperature increases with increasing concentration ratio and decreasing solid phase heat recovery effectiveness. ► Even moderate levels of heat recovery dramatically improve reactor efficiency from 3.5% to 16%.

Investigation of innovative thermochemical energy storage processes and materials for building applications

OpenAIRE

Aydin, Devrim

2016-01-01

In this study, it is aimed to develop an innovative thermochemical energy storage system through material, reactor and process based investigations for building space heating applications. The developed system could be integrated with solar thermal collectors, photovoltaic panels or heat pumps to store any excess energy in the form of heat for later use. Thereby, it is proposed to address the problem of high operational costs and CO2 emissions released by currently used fossil fuel based heat...

The NEA thermochemical database project. 30 years of accomplishments

International Nuclear Information System (INIS)

Ragoussi, Maria-Eleni; Brassinnes, Stephane

2015-01-01

The NEA Thermochemical Database (TDB) Project (www.oecd-nea.org/dbtdb/) provides a database of chemical thermodynamic values treating the most significant elements related to nuclear waste management. The work carried out since the initiation of TDB in 1984 has resulted in the publication of thirteen major reviews and a large set of selected values that have become an international reference in the field, as they are characterized for their accuracy, consistency and high quality. Herein, we describe the basis, scientific principles and organization of the TDB project, together with its evolution from its inception to the present organization as a joint undertaking under Article 5(b) of the Statute of the OECD Nuclear Energy Agency (NEA).

An approach to thermochemical modeling of nuclear waste glass

International Nuclear Information System (INIS)

Besmann, T.M.; Beahm, E.C.; Spear, K.E.

1998-01-01

This initial work is aimed at developing a basic understanding of the phase equilibria and solid solution behavior of the constituents of waste glass. Current, experimentally determined values are less than desirable since they depend on measurement of the leach rate under non-realistic conditions designed to accelerate processes that occur on a geologic time scale. The often-used assumption that the activity of a species is either unity or equal to the overall concentration of the metal can also yield misleading results. The associate species model, a recent development in thermochemical modeling, will be applied to these systems to more accurately predict chemical activities in such complex systems as waste glasses

Thermochemical properties for isooctane and carbon radicals: computational study.

Science.gov (United States)

Snitsiriwat, Suarwee; Bozzelli, Joseph W

2013-01-17

Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.

1. Thermochemical properties

International Nuclear Information System (INIS)

Rand, M.H.

1975-01-01

Thermodynamic properties (activity; molar heat capacity; free energy of reactions; partial molar free energy of solution; heat of reactions; heat of formation at 298 0 K; partial molar heat of solution; molar heat of evaporation, fusion, sublimation and transformation; standard entropy at 298 0 K; entropy of reactions; partial molar entropy of solution; molar entropy of evaporation, fusion, sublimation and transformation) of thorium, its compounds and binary alloy systems are reviewed

Experimental results of a 3 k Wh thermochemical heat storage module for space heating application

NARCIS (Netherlands)

Finck, C.J.; Henquet, E.M.R.; Soest, C.F.L. van; Oversloot, H.P.; Jong, A.J. de; Cuypers, R.; Spijker, J.C. van 't

2014-01-01

A 3 kWh thermochemical heat storage (TCS) module was built as part of an all-in house system implementation focusing on space heating application at a temperature level of 40 ºC and a temperature lift of 20 K. It has been tested and measurements showed a maximum water circuit temperature span

Cea assessment of the sulphur-iodine cycle for hydrogen production

International Nuclear Information System (INIS)

Caries, Ph.; Vitart, X.; Yvon, P.

2010-01-01

The sulphur-iodine cycle is a promising process for hydrogen production using nuclear heat: - it is a purely thermochemical cycle, implying that hydrogen production will scale with volume rather than surface; - it only involves fluids, thus avoiding the often difficult handling of solids; - its heat requirements are well matched to the temperatures available from a Generation IV very/high temperature reactor. These characteristics seem very attractive for high efficiency and low cost massive hydrogen production. On the other hand, the efficiency of the cycle may suffer from the large over-stoichiometries of water and iodine and the very important heat exchanges it involves; furthermore, due to lack of adequate thermodynamic models, its efficiency is difficult to assess with confidence. Besides, the large quantities of chemicals that need to be handled, and the corrosiveness of these chemicals, are factors not to be overlooked in terms of investment and operation costs. In order to assess the actual potential of the sulphur-iodine cycle for massive hydrogen production at a competitive cost, CEA has been conducting an important programme on this cycle, ranging from thermodynamic measurements to hydrogen production cost evaluation, with flow sheet optimisation, component sizing and investment cost estimation as intermediate steps. The paper will present the method used, the status of both efficiency and production cost estimations, and discuss perspectives for improvement. (authors)

Thermochemistry and kinetics for 2-butanone-1-yl radical (CH2·C(═O)CH2CH3) reactions with O2.

Science.gov (United States)

Sebbar, N; Bozzelli, J W; Bockhorn, H

2014-01-09

Thermochemistry of reactants, intermediates, transition state structures, and products along with kinetics on the association of CH2·C(═O)CH2CH3 (2-butanone-1-yl) with O2 and dissociation of the peroxy adduct isomers are studied. Thermochemical properties are determined using ab initio (G3MP2B3 and G3) composite methods along with density functional theory (B3LYP/6-311g(d,p)). Entropy and heat capacity contributions versus temperature are determined from structures, vibration frequencies, and internal rotor potentials. The CH2·C(═O)CH2CH3 radical + O2 association results in a chemically activated peroxy radical with 27 kcal mol(-1) excess of energy. The chemically activated adduct can react to stabilized peroxy or hydroperoxide alkyl radical adducts, further react to lactones plus hydroxyl radical, or form olefinic ketones and a hydroperoxy radical. Kinetic parameters are determined from the G3 composite methods derived thermochemical parameters, and quantum Rice-Ramsperger-Kassel (QRRK) analysis to calculate k(E) with master equation analysis to evaluate falloff in the chemically activated and dissociation reactions. One new, not previously reported, peroxy chemistry reaction is presented. It has a low barrier path and involves a concerted reaction resulting in olefin formation, H2O elimination, and an alkoxy radical.

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

Science.gov (United States)

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…

Quantifying fluctuations in reversible enzymatic cycles and clocks

Science.gov (United States)

Wierenga, Harmen; ten Wolde, Pieter Rein; Becker, Nils B.

2018-04-01

Biochemical reactions are fundamentally noisy at a molecular scale. This limits the precision of reaction networks, but it also allows fluctuation measurements that may reveal the structure and dynamics of the underlying biochemical network. Here, we study nonequilibrium reaction cycles, such as the mechanochemical cycle of molecular motors, the phosphorylation cycle of circadian clock proteins, or the transition state cycle of enzymes. Fluctuations in such cycles may be measured using either of two classical definitions of the randomness parameter, which we show to be equivalent in general microscopically reversible cycles. We define a stochastic period for reversible cycles and present analytical solutions for its moments. Furthermore, we associate the two forms of the randomness parameter with the thermodynamic uncertainty relation, which sets limits on the timing precision of the cycle in terms of thermodynamic quantities. Our results should prove useful also for the study of temporal fluctuations in more general networks.

Electrochemical study of quinone redox cycling: A novel application of DNA-based biosensors for monitoring biochemical reactions.

Science.gov (United States)

Ensafi, Ali A; Jamei, Hamid Reza; Heydari-Bafrooei, Esmaeil; Rezaei, B

2016-10-01

This paper presents the results of an experimental investigation of voltammetric and impedimetric DNA-based biosensors for monitoring biological and chemical redox cycling reactions involving free radical intermediates. The concept is based on associating the amounts of radicals generated with the electrochemical signals produced, using differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). For this purpose, a pencil graphite electrode (PGE) modified with multiwall carbon nanotubes and poly-diallydimethlammonium chloride decorated with double stranded fish sperm DNA was prepared to detect DNA damage induced by the radicals generated from a redox cycling quinone (i.e., menadione (MD; 2-methyl-1,4-naphthoquinone)). Menadione was employed as a model compound to study the redox cycling of quinones. A direct relationship was found between free radical production and DNA damage. The relationship between MD-induced DNA damage and free radical generation was investigated in an attempt to identify the possible mechanism(s) involved in the action of MD. Results showed that DPV and EIS were appropriate, simple and inexpensive techniques for the quantitative and qualitative comparisons of different reducing reagents. These techniques may be recommended for monitoring DNA damages and investigating the mechanisms involved in the production of redox cycling compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Static Thermochemical Model of COREX Melter Gasifier

Science.gov (United States)

Srishilan, C.; Shukla, Ajay Kumar

2018-02-01

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

Final Report for project titled "New fluoroionomer electrolytes with high conductivity and low SO2 crossover for use in electrolyzers being developed for hydrogen production from nuclear power plants"

Energy Technology Data Exchange (ETDEWEB)

Dennis W. Smith; Stephen Creager

2012-09-13

Thermochemical water splitting cycles, using the heat of nuclear power plants, offer an alternate highly efficient route for the production of hydrogen. Among the many possible thermochemical cycles for the hydrogen production, the sulfur-based cycles lead the competition in overall energy efficiency. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process, which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce hydrogen. The Savannah River National Laboratory (SRNL) selected the fuel cell MEA design concept for the SDE in the HyS process since the MEA concept provides a much smaller cell footprint than conventional parallel plate technology. The electrolyzer oxidizes sulfur dioxide to form sulfuric acid at the anode and reduces protons to form hydrogen at the cathode. The overall electrochemical cell reaction consists of the production of H{sub 2}SO{sub 4} and H{sub 2}. There is a significant need to provide the membrane materials that exhibit reduced sulfur dioxide transport characteristics without sacrificing other important properties such as high ionic conductivity and excellent chemical stability in highly concentrated sulfuric acid solutions saturated with sulfur dioxide. As an alternative membrane, sulfonated Perfluorocyclobutyl aromatic ether polymer (sPFCB) were expected to posses low SO2 permeability due to their stiff backbones as well as high proton conductivity, improved mechanical properties. The major accomplishments of this project were the synthesis, characterizations, and optimizations of suitable electrolyzers for good SDE performance and higher chemical stability against sulfuric acid. SDE performance results of developed sPFCB polyelectrolytes have shown that these membranes exhibit good chemical stability against H{sub 2}SO{sub 4}.

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

Science.gov (United States)

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%.

Pultrusion of a vertical axis wind turbine blade part-I: 3D thermo-chemical process simulation

NARCIS (Netherlands)

Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.; Akkerman, Remko

2015-01-01

A novel three dimensional thermo-chemical simulation of the pultrusion process is presented. A simulation is performed for the pultrusion of a NACA0018 blade profile having a curved geometry, as a part of the DeepWind project. The finite element/nodal control volume (FE/NCV) technique is used.

Pultrusion of a vertical axis wind turbine blade part-I: 3D thermo-chemical process simulation

DEFF Research Database (Denmark)

Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

2015-01-01

novel three dimensional thermo-chemical simulation of the pultrusion process is presented. A simulation is performed for the pultrusion of a NACA0018 blade profile having a curved geometry, as a part of the DeepWind project. The finite element/nodal control volume (FE/NCV) technique is used. First...

Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO{sub 2} nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Piro, M.H.A., E-mail: markuspiro@gmail.com [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Banfield, J. [Nuclear Engineering Department, University of Tennessee, Knoxville, TN (United States); Clarno, K.T., E-mail: clarnokt@ornl.gov [Reactor and Nuclear Systems Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Simunovic, S. [Computer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Besmann, T.M. [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Lewis, B.J.; Thompson, W.T. [Department of Chemistry and Chemical Engineering, Royal Military College of Canada, Kingston, ON (Canada)

2013-10-15

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 UO{sub 2}, 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 UO{sub 2} fuel with an average burnup of 102 GW d t(U){sup −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.

Crystal structure and thermochemical properties of a novel coordination compound sodium pyruvate C3H3O3Na(s)

International Nuclear Information System (INIS)

Gao, Zhen-Fei; Di, You-Ying; Liu, Su-Zhou; Lu, Dong-Fei; Dou, Jian-Min

2014-01-01

from crystallographic data. In accordance with Hess’ law, a reasonable thermochemical cycle is designed according to the practical synthesis reaction of the compound and the standard molar enthalpy of formation of the compound is calculated as an important physical quantity in chemical thermodynamics by use of an isoperibol solution-reaction calorimeter. Molar enthalpies of dissolution of the compound at various molalities are measured at T = 298.15 K in the double-distilled water. According to Pitzer’s electrolyte solution theory, molar enthalpy of dissolution of the title compound at infinite dilution is calculated to be Δ s H m ∞ = (19.81 ± 0.69) kJ · mol −1 . The values of relative apparent molar enthalpies ( Φ L) and relative partial molar enthalpies of the solvent (L ¯ 1 ) and the compound (L ¯ 2 ) at different concentrations m/(mol · kg −1 ) are derived from the experimental values of the enthalpies of dissolution of the compound

Improvement in Performance of a Thermochemical Heat Storage System by Implementing an Internal Heat Recovery System

NARCIS (Netherlands)

Gaeini, M.; Saris, L.; Zondag, H.A.; Rindt, C.C.M.

A lab-scale prototype of a thermochemical heat storage system, employing a water-zeolite 13X as the working pair, is designed and optimized for providing hot tap water. During the hydration process, humid air is introduced to the packed bed reactor filled with dehydrated zeolite 13X, and the

Optimization of waste to energy routes through biochemical and thermochemical treatment options of municipal solid waste in Hyderabad, Pakistan

International Nuclear Information System (INIS)

Korai, Muhammad Safar; Mahar, Rasool Bux; Uqaili, Muhammad Aslam

2016-01-01

Highlights: • Existing practice of municipal solid waste management of Hyderabad city, Pakistan have been analyzed. • Development of scenarios on basis of nature of waste components for optimizing waste to energy route. • Analyzing the biochemical and thermochemical potential of MSW through various scenarios. • Evaluation of various treatment technologies under scenarios to optimize waste to energy route. - Abstract: Improper disposal of municipal solid waste (MSW) has created many environmental problems in Pakistan and the country is facing energy shortages as well. The present study evaluates the biochemical and thermochemical treatment options of MSW in order to address both the endemic environmental challenges and in part the energy shortage. According to the nature of waste components, a number of scenarios were developed to optimize the waste to energy (WTE) routes. The evaluation of treatment options has been performed by mathematical equations using the special characteristics of MSW. The power generation potential (PGP) of biochemical (anaerobic digestion) has been observed in the range of 5.9–11.3 kW/ton day under various scenarios. The PGP of Refuse Derived Fuel (RDF), Mass Burn Incinerator (MBI), Gasification/Pyrolysis (Gasi./Pyro.) and Plasma Arc Gasification (PAG) have been found to be in the range of 2.7–118.6 kW/ton day, 3.8–164.7 kW/ton day, 4.2–184.5 kW/ton day and 5.2–224 kW/ton day, respectively. The highest values of biochemical and all thermochemical technologies have been obtained through the use of scenarios including the putrescible components (PCs) of MSW such as food and yard wastes, and the non-biodegradable components (NBCs) of MSW such as plastic, rubber, leather, textile and wood respectively. Therefore, routes which include these components are the optimized WTE routes for maximum PGP by biochemical and thermochemical treatments of MSW. The findings of study lead to recommend that socio-economic and environmental

Reaction of calcium chloride with alkali metal chlorides in melts

International Nuclear Information System (INIS)

Savin, V.D.; Mikhajlova, N.P.

1984-01-01

Thermochemical characteristics of CaCl 2 reaction with sodium, potassium, rubidium and cesium chlorides in melts at 890 deg C are determined. The values of formation enthalpies of infinitely diluted by CaCl 2 solutions (ΔH) in the chloride row increase from -22 in NaCl to -47 kJ/mol of CaCl 2 in CsCl. With increasing the concentration of calcium chloride in the solution the ΔH values decrease. The regularities of separation from the solution of the CaCl 2 -CsCl system at 890 deg C of the CaCl 2 x CsCl in solid are studied. Formation enthalpies under the given conditions constitutes -70+-3 kJ/mol

Mechanism of reaction and cycling behavior of nickel felt cathodes in NaAlCl4 molten salt batteries

Energy Technology Data Exchange (ETDEWEB)

Hjuler, H.A.; Knutz, B.C.; Berg, R.W.; Bjerrum, N.J.

1990-11-01

The battery system: Al/NaCl-AlCl3-Al2X3/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen have been studied at 175 deg. C. Charge/discharge experiments, performed on cells with NaCl saturated melts, show that advantages with regard to rate capability, cyclability and probably energy density can be obtained with systems containing dissolved chalcogen compared with the chalcogen free system. The cells with sulfur added to the electrolyte exhibit the same charge/discharge curves as found for comparable cells prepared with a nickel sulfide cathode. Exchange of chalcogen between cathode and molten salt during cycling was studied by performing gravimetric analysis and Raman spectroscopy of the electrolytes. In the low charge state, formation and decomposition of nickel chalcogenides, associated with uptake/release of chalcogenide from the melt, take place to a large extent during cycling. Cathode reactions were studied by comparing coulometric titrations (performed on cells with slightly acidic NACl-AlCl3 melts containing approx 0.51 mole % AlCl3 and small amounts of chalcogen) with model calculations. The model set up describes equilibrium concentrations of constituent species in the electrolyte and equilibrium potentials of the electrodes versus number of coulombs passed through the cells, assuming probable cathode reactions. (author) 27 refs.

Power efficiency improvements of the industrial processes at application of thermochemical recuperation of heath of the leaving gases with use of microchannel reactors

Science.gov (United States)

Tararykov, A. V.; Garyaev, A. B.

2017-11-01

The possibility of increasing the energy efficiency of production processes by converting the initial fuel - natural gas to synthesized fuel using the heat of the exhaust gases of plants involved in production is considered. Possible applications of this technology are given. A mathematical model of the processes of heat and mass transfer occurring in a thermochemical reactor is developed taking into account the nonequilibrium nature of the course of chemical reactions of fuel conversion. The possibility of using microchannel reaction elements and facilities for methane conversion in order to intensify the process and reduce the overall dimensions of plants is considered. The features of the course of heat and mass transfer processes under flow conditions in microchannel reaction elements are described. Additions have been made to the mathematical model, which makes it possible to use it for microchannel installations. With the help of a mathematical model, distribution of the parameters of mixtures along the length of the reaction element of the reactor-temperature, the concentration of the reacting components, the velocity, and the values of the heat fluxes are obtained. The calculations take into account the change in the thermophysical properties of the mix-ture, the type of the catalytic element, the rate of the reactions, the heat exchange processes by radiation, and the lon-gitudinal heat transfer along the flow of the reacting mixture. The reliability of the results of the application of the mathematical model is confirmed by their comparison with the experimental data obtained by Grasso G., Schaefer G., Schuurman Y., Mirodatos C., Kuznetsov V.V., Vitovsky O.V. on similar installations.

Thermodynamics and performance of the Mg-H-F system for thermochemical energy storage applications.

Science.gov (United States)

Tortoza, Mariana S; Humphries, Terry D; Sheppard, Drew A; Paskevicius, Mark; Rowles, Matthew R; Sofianos, M Veronica; Aguey-Zinsou, Kondo-Francois; Buckley, Craig E

2018-01-24

Magnesium hydride (MgH 2 ) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH 2 to form a range of Mg(H x F 1-x ) 2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H 0.85 F 0.15 ) 2 having a maximum rate of H 2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H 2 (theoretical 5.4 wt% H 2 ). An extremely stable Mg(H 0.43 F 0.57 ) 2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H 2 is not released until above 505 °C. PCI measurements of Mg(H 0.85 F 0.15 ) 2 have determined the enthalpy (ΔH des ) to be 73.6 ± 0.2 kJ mol -1 H 2 and entropy (ΔS des ) to be 131.2 ± 0.2 J K -1 mol -1 H 2 , which is slightly lower than MgH 2 with ΔH des of 74.06 kJ mol -1 H 2 and ΔS des = 133.4 J K -1 mol -1 H 2 . Cycling studies of Mg(H 0.85 F 0.15 ) 2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ∼80 °C compared to bulk MgH 2 , increasing the thermal operating temperatures for technological applications.

Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation

NARCIS (Netherlands)

Macedo, R.G.; Verhaagen, B.; Wesselink, P.R.; Versluis, Michel; van der Sluis, L.W.M.

2014-01-01

Aim To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. Methodology The root canal walls of 24 standardized root canals in

Thermodynamic analysis of a nuclear-hydrogen power system using H2/O2 direct combustion product as a working substance in the bottom cycle

International Nuclear Information System (INIS)

Chen, D.Z.; Yu, C.P.

1990-01-01

A combined thermodynamic cycle using nuclear and hydrogen energy as heat sources was investigated in this paper. The cycle is composed of top cycle using HTGR as energy source and helium as working medium and a bottom cycle with H 2 /O 2 direct combustion product as working substance. hydrogen and oxygen are thermochemically by splitting of water produced through a part of nuclear heat recovered from the top cycle. They may be delivered to the O 2 /H 2 users or used as fuels for the high temperature bottom Rankine steam cycle. The combined cycle not only uses the new energy sources instead of conventional fossil fuels but it possess the advantages of both helium and steam cycle. It has a high thermal efficiency, large unit capacity, many-sided usage and less pollution. It may represent a new type of combined cycles for future energy conversion and power generation. Using computer diagram, a variety of schemes were calculated and analyzed. The influence of some main parameters upon the cycle performance were also studied

Numerical analysis of hydrogen production via methane steam reforming in porous media solar thermochemical reactor using concentrated solar irradiation as heat source

International Nuclear Information System (INIS)

Wang, Fuqiang; Tan, Jianyu; Shuai, Yong; Gong, Liang; Tan, Heping

2014-01-01

Highlights: • H 2 production by hybrid solar energy and methane steam reforming is analyzed. • MCRT and FVM coupling method is used for chemical reaction in solar porous reactor. • LTNE model is used to study the solid phase and fluid phase thermal performance. • Modified P1 approximation programmed by UDFs is used for irradiative heat transfer. - Abstract: The calorific value of syngas can be greatly upgraded during the methane steam reforming process by using concentrated solar energy as heat source. In this study, the Monte Carlo Ray Tracing (MCRT) and Finite Volume Method (FVM) coupling method is developed to investigate the hydrogen production performance via methane steam reforming in porous media solar thermochemical reactor which includes the mass, momentum, energy and irradiative transfer equations as well as chemical reaction kinetics. The local thermal non-equilibrium (LTNE) model is used to provide more temperature information. The modified P1 approximation is adopted for solving the irradiative heat transfer equation. The MCRT method is used to calculate the sunlight concentration and transmission problems. The fluid phase energy equation and transport equations are solved by Fluent software. The solid phase energy equation, irradiative transfer equation and chemical reaction kinetics are programmed by user defined functions (UDFs). The numerical results indicate that concentrated solar irradiation on the fluid entrance surface of solar chemical reactor is highly uneven, and temperature distribution has significant influence on hydrogen production

Solar thermochemical and electrochemical research - how they can help reduce the carbon dioxide burden

Energy Technology Data Exchange (ETDEWEB)

Fletcher, E.A. [Minnesota Univ., Minneapolis, MN (United States). Dept. of Mechanical Engineering

1996-07-01

Any process which decreases the use of fossil fuels as a prime energy source will be used only if it is attractive to industry. To be attractive, an alternative energy source must be cost effective. The only alternative prime energy sources which appear likely to be cost effective in the foreseeable future are nuclear fission and the various manifestations of solar. Fission, no matter how well it is engineered on earth, can cause major disasters because of human error; its apparent cost effectiveness is illusory. Thermonuclear fusion energy is no closer to fruition than it was fifty years ago, when it was first proposed. Solar energy is thermonuclear fusion. The source is far removed from humans. We can`t manipulate the safety devices. The realization that one cannot divorce nuclear energy from the hazards of human error and malice is already a given in public policy. Being a 5800K source, solar is most efficiently used when it is directly absorbed at the site of an endothermic reaction at the highest practicable temperature. In recognizing the special thermodynamic attributes of solar energy, for the past 20 years my students and I have explored various solar thermochemical and solar thermoelectrochemical processes. This paper presents a summary of some of our pertinent observations and suggests directions that I believe future research and development should take. (UK)

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

Science.gov (United States)

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...

Toward the modeling of combustion reactions through discrete element method (DEM) simulations

Science.gov (United States)

Reis, Martina Costa; Alobaid, Falah; Wang, Yongqi

2018-03-01

In this work, the process of combustion of coal particles under turbulent regime in a high-temperature reaction chamber is modeled through 3D discrete element method (DEM) simulations. By assuming the occurrence of interfacial transport phenomena between the gas and solid phases, one investigates the influence of the physicochemical properties of particles on the rates of heterogeneous chemical reactions, as well as the influence of eddies present in the gas phase on the mass transport of reactants toward the coal particles surface. Moreover, by considering a simplistic chemical mechanism for the combustion process, thermochemical and kinetic parameters obtained from the simulations are employed to discuss some phenomenological aspects of the combustion process. In particular, the observed changes in the mass and volume of coal particles during the gasification and combustion steps are discussed by emphasizing the changes in the chemical structure of the coal. In addition to illustrate how DEM simulations can be used in the modeling of consecutive and parallel chemical reactions, this work also shows how heterogeneous and homogeneous chemical reactions become a source of mass and energy for the gas phase.

Sustainable energy with thermochemical storage; Duurzame energie met thermochemische opslag

Energy Technology Data Exchange (ETDEWEB)

Bakker, M. [ECN Efficiency and Infrastructure, Petten (Netherlands)

2010-03-15

The Energy research Centre of the Netherlands ECN) foresees an important role for heat in sustainable construction of buildings. Using salt hydrates the surplus of heat can be stored in the summer which then can be used in the winter. By means of thermochemical storage natural gas for heating tap water or houses is no longer necessary. [Dutch] Energieonderzoek Centrum Nederland (ECN) ziet voor warmteopslag een belangrijke rol weggelegd in het duurzaam bouwen. Met behulp van zouthydraten kan de overtollige warmte in de zomer opgeslagen worden om deze in de winter weer vrij te maken. Met deze thermochemische opslag is in de nabije toekomst aardgas overbodig voor de verwarming van kraanwater of woonhuis.

Thermochemical storage for long‐term low‐temperature applications : a review on current research at material and prototype scales

NARCIS (Netherlands)

Scapino, L.; Zondag, H.A.; van Bael, J.; Diriken, J.; Rindt, C.C.M.

2016-01-01

Thermochemical heat storage has the potential to store large amount of energy from renewables and other intermittent distributed sources, ideally without losses typical of sensible heat storage. owever, in order to have a commercially attractive system able to compete with conventional storage

Feasibility and comparative studies of thermochemical liquefaction of Camellia oleifera cake in different supercritical organic solvents for producing bio-oil

International Nuclear Information System (INIS)

Chen, Hongmei; Zhai, Yunbo; Xu, Bibo; Xiang, Bobin; Zhu, Lu; Li, Ping; Liu, Xiaoting; Li, Caiting; Zeng, Guangming

2015-01-01

Highlights: • Thermochemical liquefaction of COC was a prominent process for producing bio-oil. • Type of solvent affected the yield and composition of bio-oil considerably. • Liquefaction of COC in SCEL at 300 °C was preferred for producing bio-oil. - Abstract: Thermochemical liquefaction of Camellia oleifera cake (COC) for producing bio-oil was conducted in supercritical methanol (SCML), ethanol (SCEL) and acetone (SCAL), respectively. GC–MS, elemental analysis and ICP-OES were used to characterize properties of bio-oil. Results showed that thermochemical liquefaction of COC was a prominent process for generating bio-oil. Increase of temperature was beneficial to the increase of bio-oil yield, and yield of bio-oil followed the sequence of SCAL > SCEL > SCML. In spite of the highest bio-oil yield, the lowest calorific value and highest contents of Zn, Pb, Cd, Ni, Fe, Mn, and Cr were found in bio-oil from SCAL. Though SCML has very similar bio-oil composition and calorific value with SCEL, higher bio-oil yield and lower contents of heavy metals could be obtained with SCEL, especially in bio-oil from SCEL at 300 °C. Moreover, the origin of ethanol could make the bio-oil product totally renewable. Therefore, liquefaction of COC in SCEL at 300 °C could have great potential in generating bio-oil

Evaluation of potential reaction mechanisms leading to the formation of coniferyl alcohol α-linkages in lignin: a density functional theory study.

Science.gov (United States)

Watts, Heath D; Mohamed, Mohamed Naseer Ali; Kubicki, James D

2011-12-21

Five potential reaction mechanisms, each leading to the formation of an α-O-4-linked coniferyl alcohol dimer, and one scheme leading to the formation of a recently proposed free-radical coniferyl alcohol trimer were assessed using density functional theory (DFT) calculations. These potential reaction mechanisms were evaluated using both the calculated Gibbs free energies, to predict the spontaneity of the constituent reactions, and the electron-density mapped Fukui function, to determine the most reactive sites of each intermediate species. The results indicate that each reaction in one of the six mechanisms is thermodynamically favorable to those in the other mechanisms; what is more, the Fukui function for each free radical intermediate corroborates with the thermochemical results for this mechanism. This mechanism proceeds via the formation of two distinct free-radical intermediates, which then react to produce the four α-O-4 stereoisomers.

Experimental studies of an optimal operating condition for the Bunsen process in the I-S thermochemical cycle

International Nuclear Information System (INIS)

Yoon, Ho Joon; No, Hee Cheon; Kim, Young Soo; Jin, Hyung Gon; Lee, Jeong Ik; Lee, Byung Jin

2009-01-01

Conventional I-S cycles have critical limitations in material integrity and thermal efficiency. The HIx and sulfuric acids in high temperature and pressure cause serious material corrosions. They also carry too much water and iodine over the entire processes. To try to find a solution to these problems, KAIST proposed an optimal operating condition of Bunsen section through a parametric study of existing experimental data, and, based on it, devised a new flowsheet. When the contents of water and I 2 in the feed are controlled within the optimal band, HI concentration in HIx phase becomes strongly over-azeotropic. By simple flashing of the over-azeotropic HI solution, highly enriched HI vapor can be obtained, which leads to improved energy efficiency of the cycle. Since the cycle is operable under low pressures, the corrosivity of the operating condition can also be alleviated. In order to validate the previous experimental data and enhance the feasibility of the newly proposed flowsheet, KAIST is performing experiments. Procedure and results of early stage of experiments are introduced in this paper. (author)

Thermochemical parameters of caffeine, theophylline, and xanthine

Energy Technology Data Exchange (ETDEWEB)

Ngo Tuan Cuong; Truong Ba Tai [Department of Chemistry, and Mathematical Modeling and Computational Science Center (LMCC), Katholieke Universiteit Leuven, B-3001 Leuven (Belgium); Vu Thi Thu Ha [Institute of Chemistry, Vietnam Academy of Science and Technology, Hanoi (Viet Nam); Minh Tho Nguyen, E-mail: minh.nguyen@chem.kuleuven.b [Department of Chemistry, and Mathematical Modeling and Computational Science Center (LMCC), Katholieke Universiteit Leuven, B-3001 Leuven (Belgium)

2010-04-15

Thermochemical parameters of caffeine 1, theophylline 2, xanthine 3, uracil, and imidazole derivatives are determined by quantum chemical calculations. Using the composite G3B3 method, the standard heat of formation of caffeine in the gaseous phase amounts to DELTA{sub f}H{sub g}{sup 0}(1)=-243+-8kJ.mol{sup -1}, which lends a support for the recent experimental value of -237.0 +- 2.5 kcal . mol{sup -1}. We also obtain DELTA{sub f}H{sub g}{sup 0}(2)=-232+-8kJ.mol{sup -1}andDELTA{sub f}H{sub g}{sup 0}(3)=-209+-8kJ.mol{sup -1}. The adiabatic ionization energies are IE{sub a}(1) = 7.9 eV, IE{sub a}(2) = 8.1 eV, and IE{sub a}(3) = 8.5 eV using B3LYP calculations. The enhanced ability of caffeine to eject electron, as compared to the parent compounds and cyclic components, is of interest with regard to its potential use as a corrosion inhibitor.

Thermochemical investigations on uranyl phosphates and arsenates

International Nuclear Information System (INIS)

Barten, H.

1986-01-01

Results are described of a study of the thermochemical stability of anhydrous phosphates and arsenates. The results of phase studies deal with compound formation and characterization, coexisting phases and limiting physical or chemical properties. The uranyl phosphates evolve oxygen at higher temperatures and the arsenates lose arsenic oxide vapour. These phenomena give the possibility to describe their thermodynamic stabilities. Thus oxygen pressures of uranyl phosphates have been measured using a static, non-isothermal method. Having made available the pure anhydrous compounds in the course of this investigation, molar thermodynamic quantities have been measured as well. These include standard enthalpies of formation from solution calorimetry and high-temperature heat-capacity functions derived from enthalpy increments measured. Some attention is given to compounds with uranium in valencies lower than six which have been met during the investigation. An evaluation is made of the thermodynamics of the compounds studied, to result in tabulized high-temperature thermodynamic functions. Relative stabilities within the systems are discussed and comparisons of the uranyl phosphates and the arsenates are made. (Auth.)

Review and analysis of the 1980-1989 biomass thermochemical conversion program

Energy Technology Data Exchange (ETDEWEB)

Stevens, D.J.

1994-09-01

In the period between 1980 and 1989, the U.S. Department of Energy (DOE) sponsored research and development projects through its Biomass Thermochemical Conversion (BTC) Program. Thermochemical conversion technologies use elevated temperatures to convert biomass into more useful forms of energy such as fuel gases or transportation fuels. The BTC Program included a wide range of biomass conversion projects in the areas of gasification, pyrolysis, liquefaction, and combustion. This work formed the basis of the present DOE research and development efforts on advanced liquid fuel and power generation systems. At the beginning of Fiscal Year 1989, the management of the BTC Program was transferred from Pacific Northwest Laboratory (PNL) to National Renewable Energy Laboratory (NREL, formerly Solar Energy Research Institute). This document presents a summary of the research which was performed under the BTC Program during the 1981-1989 time frame. The document consists of an analysis of the research projects which were funded by the BTC Program and a bibliography of published documents. This work will help ensure that information from PNL`s BTC Program is available to those interested in biomass conversion technologies. The background of the BTC Program is discussed in the first chapter of this report. In addition, a brief summary of other related biomass research and development programs funded by the U.S. Department of Energy and others is presented with references where additional information can be found. The remaining chapters of the report present a detailed summary of the research projects which were funded by the BTC Program. The progress which was made on each project is summarized, the overall impact on biomass conversion is discussed, and selected references are provided.

Chemistry of sustainability-Part I: Carbon dioxide as an organic synthon and Part II: Study of thermodynamics of cation exchange reactions in semiconductor nanocrystals

Science.gov (United States)

Sathe, Ajay A.

Sustainability is an important part of the design and development of new chemical and energy conversion processes. Simply put sustainability is the ability to meet our needs without sacrificing the ability of the next generations to meet theirs. This thesis describes our efforts in developing two orthogonal strategies for the fixation of CO2 by utilizing high energy intermediates which are generated via oxidative or reductive processes on common organic substrates and of thermochemical measurements of cation exchange reactions which will aid the development of new materials relevant for energy conversion and storage. The first chapter lays a background for the challenges and opportunities for the use of CO2 in organic synthesis. The rapidly growing field of continuous flow processing in organic synthesis is introduced, and its importance in the development of sustainable chemical conversions is highlighted. The second chapter describes the development of a novel route to alpha-amino acids via reductive carboxylation of imines. A mechanistic proposal is presented and the reaction is shown to proceed through the intermediacy of alpha-amino alkyl metal species. Possible strategies for designing catalytic and enantioselective variants of the reaction are presented. The third chapter describes the development of a catalytic oxidative carboxylation of olefins to yield cyclic carbonates. The importance of flow chemistry and membrane separation is demonstrated by allowing the combination of mutually incompatible reagents in a single reaction sequence. While the use of carbon dioxide for synthesis of organic fine chemicals is not expected to help reduce the atmospheric carbon dioxide levels, or tackle climate change, it certainly has the potential to reduce our dependence on non-sustainable carbon feedstocks, and help achieve a carbon neutral chemical life cycle. Having described the use of carbon dioxide and flow chemistry for sustainable chemical conversion, the fourth

Thermo-chemical characterization of a Al nanoparticle and NiO nanowire composite modified by Cu powder

International Nuclear Information System (INIS)

Bohlouli-Zanjani, Golnaz; Wen, John Z.; Hu, Anming; Persic, John; Ringuette, Sophie; Zhou, Y. Norman

2013-01-01

Highlights: • First study on the copper modified powder-type Al nanoparticle and NiO nanowire composites. • Experimental findings were unique in identifying the AlNi formation and comparing with the Al/CuO thermite. • Potential applications in material joining and bonding. - Abstract: Thermo-chemical properties of the Al nanoparticle and NiO nanowire composites modified by the micro-sized copper additive were investigated experimentally. Their onset temperatures of ignition and energy release data per mass were characterized using differential thermal analysis measurements. These microstructures and chemical compositions of reaction products were analyzed using scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. The fuel-rich Al/NiO/Cu composites produced two types of metallic spheres. Copper spheres were formed from melting and solidification of the copper additive, while AlNi composite spheres were identified by the energy dispersive X-ray spectroscopy and X-ray diffraction analyses. It was found that the amount of the copper additive did not significantly influence the onset temperature of thermite peaks, but caused a dramatic change in energy release. The aforementioned ignition and energetic properties were compared with these from the Al nanoparticle and CuO nanowire composites

Crystal structure and thermochemical properties of n-decylammonium ethyl sulfate (C10H21NH3SO4C2H5)(s)

International Nuclear Information System (INIS)

Zhang, Li-Jun; Di, You-Ying; Dou, Jian-Min

2013-01-01

the solvent at different concentrations were derived from experimental values of enthalpies of dissolution of the compound. Finally, enthalpies of hydration of the compound and its anion were calculated by designing a thermochemical cycle in accordance with lattice potential energy and molar enthalpy of dissolution at infinite dilution.

Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0(2,6)]decane.

Science.gov (United States)

Hudzik, Jason M; Castillo, Álvaro; Bozzelli, Joseph W

2015-09-24

Exo-tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is an interesting strained ring compound and the single-component high-energy density hydrocarbon fuel known as JP-10. Important initial reactions of TCD at high temperatures could cleave a strained carbon-carbon (C-C) bond in the ring system creating diradicals also constrained by the remaining ring system. This study determines the thermochemical properties of these diradicals (TCD-H2 mJ-nJ where m and n correspond to the cleaved carbons sites) including the carbon-carbon bond dissociation energy (C-C BDE) corresponding to the cleaved TCD site. Thermochemical properties including enthalpies (ΔH°f298), entropies (S(T)), heat capacities (Cp(T)), and C-H and C-C BDEs for the parent (TCD-H2 m-n), radical (TCD-H2 mJ-n and m-nJ), diradical (TCD-H2 mJ-nJ), and carbene (TCD-H2 mJJ-n and m-nJJ) species are determined. Structures, vibrational frequencies, moments of inertia, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2 m-n parent and radical species are determined using the B3LYP density functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods. For singlet and triplet TCD diradicals and carbenes, M06-2X, ωB97X-D, and CCSD(T) methods are included in the analysis to determine ΔH°f298 values. The C-C BDEs are further calculated using CASMP2(2,2)/aug-cc-pvtz//CASSCF(2,2)/cc-pvtz and with the CASMP2 energies extrapolated to the complete basis set limit. The bond energies calculated with these methods are shown to be comparable to the other calculation methods. Isodesmic work reactions are used for enthalpy analysis of these compounds for effective cancelation of systematic errors arising from ring strain. C-C BDEs range from 77.4 to 84.6 kcal mol(-1) for TCD diradical singlet species. C-H BDEs for the parent TCD-H2 m-n carbon sites range from 93 to 101 kcal mol(-1) with a

The behaviour of radionuclides in gas adsorption chromatographic processes with superimposed chemical reactions (chlorides)

International Nuclear Information System (INIS)

Eichler, B.

1996-01-01

Thermochemical relationships are derived describing the gas adsorption chromatographic transport of carrier-free radionuclides. Especially, complex adsorption processes such as dissociative, associative and substitutive adsorption are dealt with. The comparison of experimental with calculated data allows the determination of the type of adsorption reaction, which is the basis of the respective gas chromatographic process. The behaviour of carrier-free radionuclides of elements Pu, Ce, Ru, Co and Cr in thermochromatographic experiments with chlorinating carrier gases can be described as dissociative adsorption of chlorides in higher oxidation states. The gas adsorption chromatographic transport of Zr with oxygen and chlorine containing carrier gas is shown to be a substitutive adsorption process. The consequences of superimposed chemical reactions on the interpretation of results and the conception of gas adsorption chromatographic experiments with carrier-free radionuclides in isothermal columns and in temperature gradient tubes is discussed. (orig.)

Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

International Nuclear Information System (INIS)

Haas, P.A.

1992-02-01

The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl 4 ) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO 2 ) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl 4 -UO 2 shows a reaction to form uranium oxychloride (UOCl 2 ) that has a good solubility in molten UCl 4 . This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl 4 , ZrCl 4 , SiCl 4 , ThCl 4 ) by reaction of oxides with chlorine (Cl 2 ) and carbon has application to the preparation of UCl 4

FY 1974 report on the results of the Sunshine Project. Study of the hydrogen production technology (Study of the hydrogen production technology by thermochemical method); 1974 nendo suiso no seizo gijutsu no kenkyu seika hokokusho. Netsukagakuho ni yoru suiso seizo gijutsu no kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1975-05-30

For the purpose of developing a new hydrogen production technology, a feasibility study was made of the copper-halogen system and alkali carbonate-iodine system processes presented as a new thermochemical process from viewpoints of the progress of reaction, side reaction, reaction yield, thermal efficiency, etc. The study went forward smoothly, has achieved the target in the early stage, and has been finished. In the study of optimal conditions of the process, the progress of each unit reaction was experimentally confirmed. By measuring the reaction yield, optimal reaction conditions for expediting the reaction were found out. As a result, it was found that the proposed processes proposed both advance rather easily, and was thought that those are worthy of making further engineering study. In the study of improvement and optimization of the process, since some altered processes are considered for the processes presented, an investigational study was made on a method to calculate thermal efficiency which is one of the standards for the process evaluation, and thermal efficiencies in various processes were trially calculated, based on the calculating method. As a result, it was thought that this process is equal to other processes. (NEDO)

Hydrogen and oxygen production with nuclear heat

International Nuclear Information System (INIS)

Barnert, H.

1979-09-01

After some remarks on the necessity of producing secondary energy sources for the heat market, the thermodynamic fundamentals of the processes for producing hydrogen and oxygen from water on the basis of nuclear thermal energy are briefly explained. These processes are summarized as one class of the 'thermochemical cycle process' for the conversion of thermal into chemical energy. A number of thermochemical cycle processes are described. The results of the design work so far are illustrated by the example of the 'sulphuric acid hybrid process'. The nuclear heat source of the thermochemical cycle process is the high-temperature reactor. Statements concerning rentability are briefly commented upon, and the research and development efforts and expenditure required are sketched. (orig.) 891 GG/orig. 892 MB [de

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

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

Calderoni, Pattrick

2010-01-01

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 reactor 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 homogeneous 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 and 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

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

Energy Technology Data Exchange (ETDEWEB)

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 reactor 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

Achievement report for fiscal 1976 on Sunshine Program. Research on hydrogen production technology (Research on hydrogen production technology using thermochemical method); 1976 nendo suiso no seizo gijutsu no kenkyu seika hokokusho. Netsukagakuho ni yoru suiso seizo gijutsu no kenkyu

Energy Technology Data Exchange (ETDEWEB)

NONE

1977-03-01

This report covers part of the efforts to develop new hydrogen production technologies. Out of many processes involving Cu-halogen and alkali carbonate-iodine systems proposed as novel thermochemical processes, after they are compared with each other, a process of a sodium carbonate-iodine system with nickel in between is chosen. The chosen process is deemed to be the most excellent among the processes disclosed up to fiscal 1975. A feasibility study is conducted for the chosen process from the viewpoint of reaction rate, separation of reactive substances from each other, method for reaction manipulation, materials for device constitution, and thermal efficiency. As for the measurement of reaction rate for each unit reaction, basic reaction data are determined centering about the nickel iodide decomposition reaction and the sodium iodide carbonation reaction, and then reaction conditions which are roughly satisfying are obtained. A larger reaction unit is built in which the amounts of substances that come into reaction are approximately 10 times larger than those in the ones used in basic experiments. The progress of reactions is observed in the reaction unit, with the size enlarged in preparation for future construction of still larger reaction units. Methods for selectively isolating hydrogen out of gases ensuing from the decomposition are evaluated from the viewpoint of energy efficiency. In the selection of a reaction manipulation method, a single unit reaction process is advocated, and its thermal efficiency is estimated. (NEDO)

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

Science.gov (United States)

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

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.

Spectrographic determination of boron and silicon in uranium tetrafluoride: Study of the chemical reactions in the electrode cavity when ZnO is used as a uranium excitation suppressor

International Nuclear Information System (INIS)

Alduan, F. A.; Capdevila, C.; Roca, M.

1973-01-01

A method has been developed for determining traces of boron and silicon in uranium tetrafluoride. Use is made of zinc oxide to decrease the volatilization of uranium and achieve high sensitivities. The thermochemical reactions which occur in the anode cavity during the arcing process have been investigated. UO 2 and a uranium, zinc and fluorine compound, both less volatile than uranium tetrafluoride, are formed. (Author)

Renewable energy from corn residues by thermochemical conversion

Science.gov (United States)

Yu, Fei

Declining fossil oil reserve, skyrocket price, unsecured supplies, and environment pollution are among the many energy problems we are facing today. It is our conviction that renewable energy is a solution to these problems. The long term goal of the proposed research is to develop commercially practical technologies to produce energy from renewable resources. The overall objective of my research is to study and develop thermochemical processes for converting bulky and low-energy-density biomass materials into bio-fuels and value-added bio-products. The rationale for the proposed research is that, once such processes are developed, processing facility can be set up on or near biomass product sites, reducing the costs associated with transport of bulky biomass which is a key technical barrier to biomass conversion. In my preliminary research, several conversion technologies including atmospheric pressure liquefaction, high pressure liquefaction, and microwave pyrolysis have been evaluated. Our data indicated that microwave pyrolysis had the potential to become a simple and economically viable biomass conversion technology. Microwave pyrolysis is an innovative process that provides efficient and uniform heating, and are robust to type, size and uniformity of feedstock and therefore suitable for almost any waste materials without needing to reduce the particle size. The proposed thesis focused on in-depth investigations of microwave pyrolysis of corn residues. My first specific aim was to examine the effects of processing parameters on product yields. The second specific research aim was to characterize the products (gases, bio-oils, and solid residues), which was critical to process optimization and product developments. Other research tasks included conducting kinetic modeling and preliminary mass and energy balance. This study demonstrated that microwave pyrolysis could be optimized to produce high value syngas, liquid fuels and pyrolytic carbons, and had a great

Energy efficient thermochemical conversion of very wet biomass to biofuels by integration of steam drying, steam electrolysis and gasification

DEFF Research Database (Denmark)

Clausen, Lasse Røngaard

2017-01-01

A novel system concept is presented for the thermochemical conversion of very wet biomasses such as sewage sludge and manure. The system integrates steam drying, solid oxide electrolysis cells (SOEC) and gasification for the production of synthetic natural gas (SNG). The system is analyzed...

Metabolic Interaction between Urea Cycle and Citric Acid Cycle Shunt: A Guided Approach

Science.gov (United States)

Pesi, Rossana; Balestri, Francesco; Ipata, Piero L.

2018-01-01

This article is a guided pedagogical approach, devoted to postgraduate students specializing in biochemistry, aimed at presenting all single reactions and overall equations leading to the metabolic interaction between ureagenesis and citric acid cycle to be incorporated into a two-three lecture series about the interaction of urea cycle with other…

Upper mantle compositional variations and discontinuity topography imaged beneath Australia from Bayesian inversion of surface-wave phase velocities and thermochemical modeling

DEFF Research Database (Denmark)

Khan, A.; Zunino, Andrea; Deschamps, F.

2013-01-01

Here we discuss the nature of velocity heterogeneities seen in seismic tomography images of Earth's mantle whose origins and relation to thermochemical variations are yet to be understood. We illustrate this by inverting fundamental-mode and higher-order surface-wave phase velocities for radial....../Fe and Mg/Si values relative to surrounding mantle. Correlated herewith are thermal variations that closely follow surface tectonics. We also observe a strong contribution to lateral variations in structure and topography across the “410 km” seismic discontinuity from thermochemically induced phase......-wave tomography models with other regional models is encouraging. Radial anisotropy is strongest at 150/200 km depth beneath oceanic/continental areas, respectively, and appears weak and homogeneous below. Finally, geoid anomalies are computed for a subset of sampled model and compared to observations....

Demonstration of a 100-kWth high-temperature solar thermochemical reactor pilot plant for ZnO dissociation

Science.gov (United States)

Koepf, E.; Villasmil, W.; Meier, A.

2016-05-01

Solar thermochemical H2O and CO2 splitting is a viable pathway towards sustainable and large-scale production of synthetic fuels. A reactor pilot plant for the solar-driven thermal dissociation of ZnO into metallic Zn has been successfully developed at the Paul Scherrer Institute (PSI). Promising experimental results from the 100-kWth ZnO pilot plant were obtained in 2014 during two prolonged experimental campaigns in a high flux solar simulator at PSI and a 1-MW solar furnace in Odeillo, France. Between March and June the pilot plant was mounted in the solar simulator and in-situ flow-visualization experiments were conducted in order to prevent particle-laden fluid flows near the window from attenuating transparency by blocking incoming radiation. Window flow patterns were successfully characterized, and it was demonstrated that particle transport could be controlled and suppressed completely. These results enabled the successful operation of the reactor between August and October when on-sun experiments were conducted in the solar furnace in order to demonstrate the pilot plant technology and characterize its performance. The reactor was operated for over 97 hours at temperatures as high as 2064 K; over 28 kg of ZnO was dissociated at reaction rates as high as 28 g/min.

Carbon Dioxide Shuttling Thermochemical Storage Using Strontium Carbonate

Energy Technology Data Exchange (ETDEWEB)

Mei, Renwei [Univ. of Florida, Gainesville, FL (United States). Dept. of Mechanical and Aerospace Engineering

2015-06-15

Phase I concludes with significant progress made towards the SunShot ELEMENTS goals of high energy density, high power density, and high temperature by virtue of a SrO/SrCO₃ based material. A detailed exploration of sintering inhibitors has been conducted and relatively stable materials supported by YSZ or SrZO₃ have been identified as the leading candidates. In 15 cycle runs using a 3 hour carbonation duration, several materials demonstrated energy densities of roughly 1500 MJ/m³ or greater. The peak power density for the most productive materials consistently exceeded 40 MW/m³—an order of magnitude greater than the SOPO milestone. The team currently has a material demonstrating nearly 1000 MJ/m³ after 100 abbreviated (1 hour carbonation) cycles. A subsequent 8 hour carbonation after the 100 cycle test exhibited over 1500 MJ/m³, which is evidence that the material still has capacity for high storage albeit with slower kinetics. Kinetic carbonation experiments have shown three distinct periods: induction, kinetically-controlled, and finally a diffusion-controlled period. In contrast to thermodynamic equilibrium prediction, higher carbonation temperatures lead to greater conversions over a 1 hour periods, as diffusion of CO₂ is more rapid at higher temperatures. A polynomial expression was fit to describe the temperature dependence of the linear kinetically-controlled regime, which does not obey a traditional Arrhenius relationship. Temperature and CO₂ partial pressure effects on the induction period were also investigated. The CO₂ partial pressure has a strong effect on the reaction progress at high temperatures but is insignificant at temperatures under 900°C. Tomography data for porous SrO/SrCO₃ structures at initial stage and after multiple carbonation/decomposition cycles have been obtained. Both 2D slices and 3D reconstructed representations have

Holistic analysis of thermochemical processes by using solid biomass for fuel production in Germany; Ganzheitliche Analyse thermochemischer Verfahren bei der Nutzung fester Biomasse zur Kraftstoffproduktion in Deutschland

Energy Technology Data Exchange (ETDEWEB)

Henssler, Martin

2015-04-28

According to the German act ''Biokraftstoff-Nachhaltigkeitsverordnung'', biofuels must show a CO{sub 2eq}-reduction compared to the fossil reference fuel (83.8 g CO{sub 2eq}/MJ{sub fuel} /Richtlinie 98/70/EG/) of 35 % beginning with 2011. In new plants, which go into operation after the 31.12.2016 the CO{sub 2eq}-savings must be higher than 50 % in 2017 and higher than 60 % in 2018 /Biokraft-NachV/. The biofuels (methyl ester of rapeseed, bioethanol and biomethane) considered in this study do not meet these requirements for new plants. To comply with these rules new processes must be deployed. Alternative thermochemical generated fuels could be an option. The aim of this work is to evaluate through a technical, ecological and economic analysis (Well-to-Wheel) whether and under what conditions the thermochemical production of Fischer-Tropsch-diesel or -gasoline, hydrogen (H{sub 2}) and Substitute Natural Gas (SNG) complies with the targets. Four different processes are considered (fast pyrolysis and torrefaction with entrained flow gasifier, CHOREN Carbo-V {sup registered} -gasifier, Absorption Enhanced Reforming (AER-) gasifier). Beside residues such as winter wheat straw and residual forest wood, wood from short-rotation plantations is taken into account. The technical analysis showed that at present status (2010) two and in 2050 six plants can be operated energy-self-sufficient. The overall efficiency of the processes is in the range of 41.5 (Fischer-Tropsch-diesel or -gasoline) and 59.4 % (H{sub 2}). Furthermore, it was found that for 2010, all thermochemical produced fuels except the H{sub 2}-production from wood from short-rotation plantations in decentralised or central fast pyrolysis and in decentralised torrefactions with entrained flow gasifier keep the required CO{sub 2eq}-saving of 60 %. In 2050, all thermochemical produced fuels will reach these limits. The CO{sub 2eq}-saving is between 72 (H{sub 2}) and 95 % (Fischer

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

Science.gov (United States)

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

2016-05-01

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

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

Science.gov (United States)

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.

Hydrogen production from biomass by thermochemical recuperative energy conversion

Energy Technology Data Exchange (ETDEWEB)

Fushimi, C.; Araki, K.; Yamaguchi, Y.; Tsutsumi, A. [Tokyo Univ. (Japan). Dept. of Chemical System Engineering

2002-07-01

The authors conducted, using a thermogravimetric reactor, a kinetic study of production of thermochemical recuperative hydrogen from biomass. The four different biomass materials used were: cellulose, lignin, metroxylon stem, and coconut husk. Under both rapid heating and slow heating conditions, the weight changes of the biomass samples during the steam gasification or pyrolysis were measured at 973 Kelvin. Simultaneously, measurements of the evolution rates of low-molecular-weight gas products such as hydrogen, methane, carbon monoxide, and carbon dioxide were taken with the help of a mass spectrometer and a micro gas chromatograph (GC). The steam gasification of char significantly increased the amount of hydrogen and carbon dioxide production. The results also indicated that at higher heating rate, the cold gas efficiency of steam gasification was increased. This can be explained by the suppression of the tar production at lower temperature. 25 refs., 2 tabs., 10 figs.

Thermochemistry of ionic liquid-catalysed reactions. Isomerisation and transalkylation of tert-alkyl-benzenes. Are these systems ideal?

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Emel'yanenko, Vladimir N.; Hopmann, Elisabeth; Arlt, Wolfgang

2010-01-01

The chemical equilibrium of mutual interconversions of tert-alkyl-benzenes was studied in the temperature range (286 to 423) K using chloroaluminate ionic liquids as a catalyst. The knowledge of the activity coefficients is required in order to obtain the thermodynamic equilibrium constants K a . A well established procedure, COSMO-RS, has been used to assess activity coefficients of the reaction participants in the liquid phase. Enthalpies of five reactions of isomerisation and transalkylation of tert-alkyl-benzenes were obtained from temperature dependences of the corresponding equilibrium constants in the liquid phase. For the sake of comparison, high-level ab initio calculations of the reaction participants have been performed using the Gaussian-03 program package. Absolute electronic energy values of the molecules have been obtained using B3LYP and G3MP2 level. Using these results enthalpies of reaction of isomerisation and transalkylation of tert-alkyl-benzenes in the liquid phase based on the first principles are found to be in good agreement with the data obtained from the thermochemical measurements.

Methods for estimating the enthalpy of formation of inorganic compounds; thermochemical and crystallographic investigations of uranyl salts of group VI elements

International Nuclear Information System (INIS)

Brandenburg, N.P.

1978-01-01

The first part of this thesis is concerned with parameter methods for estimating the standard enthalpy of formation, ΔH 0 sub(f), of inorganic compounds. In this type of method the estimate is a function of parameters, assigned to cation and anion, respectively. The usefulness of a new estimation method is illustrated in the case of uranyl sulphide. In the second part of this thesis crystallographic and thermochemical properties of uranyl salts of group VI elements are described. Crystal structures are given for β-UO 2 SO 4 , UO 2 SeO 3 , and α-UO 2 SeO 4 . Thermochemical measurements have been restricted to the determination of ΔH 0 sub(f)(UO 2 SO 3 ) and ΔH 0 sub(f)(UO 2 TeO 3 ) by means of isoperibol solution calorimetry. (Auth.)

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

Energy Technology Data Exchange (ETDEWEB)

Dubois, Vincent, E-mail: vincent-jp.dubois@cea.fr; Pineau, Nicolas [CEA, DAM, DIF, F-91297 Arpajon (France)

2016-01-07

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.

Literature information applicable to the reaction of uranium oxides with chlorine to prepare uranium tetrachloride

Energy Technology Data Exchange (ETDEWEB)

Haas, P.A.

1992-02-01

The reaction of uranium oxides and chlorine to prepare anhydrous uranium tetrachloride (UCl{sub 4}) are important to more economical preparation of uranium metal. The most practical reactions require carbon or carbon monoxide (CO) to give CO or carbon dioxide (CO{sub 2}) as waste gases. The chemistry of U-O-Cl compounds is very complex with valances of 3, 4, 5, and 6 and with stable oxychlorides. Literature was reviewed to collect thermochemical data, phase equilibrium information, and results of experimental studies. Calculations using thermodynamic data can identify the probable reactions, but the results are uncertain. All the U-O-Cl compounds have large free energies of formation and the calculations give uncertain small differences of large numbers. The phase diagram for UCl{sub 4}-UO{sub 2} shows a reaction to form uranium oxychloride (UOCl{sub 2}) that has a good solubility in molten UCl{sub 4}. This appears more favorable to good rates of reaction than reaction of solids and gases. There is limited information on U-O-Cl salt properties. Information on the preparation of titanium, zirconium, silicon, and thorium tetrachlorides (TiCl{sub 4}, ZrCl{sub 4}, SiCl{sub 4}, ThCl{sub 4}) by reaction of oxides with chlorine (Cl{sub 2}) and carbon has application to the preparation of UCl{sub 4}.

Thermochemical study of cyanopyrazines: Experimental and theoretical approaches

International Nuclear Information System (INIS)

Miranda, Margarida S.; Morais, Victor M.F.; Matos, M. Agostinha R.

2006-01-01

The standard (p - bar =0.1MPa) molar energy of combustion, at T=298.15K, of crystalline 2,3-dicyanopyrazine was measured by static bomb calorimetry, in oxygen atmosphere. The standard molar enthalpy of sublimation, at T=298.15K, was obtained by Calvet Microcalorimetry, allowing the calculation of the standard molar enthalpy of formation of the compound, in the gas phase, at T=298.15K: Δ f H m - bar (g)=(518.7+/-3.4)kJ.mol -1 . In addition, the geometries of all cyanopyrazines were obtained using density functional theory with the B3LYP functional and two basis sets: 6-31G* and 6-311G**. These calculations were then used for a better understanding of the relation between structure and energetics of the cyanopyrazine systems. These calculations also reproduce measured standard molar enthalpies of formation with some accuracy and do provide estimates of this thermochemical parameter for those compounds that could not be studied experimentally, namely the tri- and tetracyanopyrazines: the strong electron withdrawing cyano group on the pyrazine ring makes cyanopyrazines highly destabilized compounds

Thermal energy storage using thermo-chemical heat pump

International Nuclear Information System (INIS)

Hamdan, M.A.; Rossides, S.D.; Haj Khalil, R.

2013-01-01

Highlights: ► Understanding of the performance of thermo chemical heat pump. ► Tool for storing thermal energy. ► Parameters that affect the amount of thermal stored energy. ► Lithium chloride has better effect on storing thermal energy. - Abstract: A theoretical study was performed to investigate the potential of storing thermal energy using a heat pump which is a thermo-chemical storage system consisting of water as sorbet, and sodium chloride as the sorbent. The effect of different parameters namely; the amount of vaporized water from the evaporator, the system initial temperature and the type of salt on the increase in temperature of the salt was investigated and hence on the performance of the thermo chemical heat pump. It was found that the performance of the heat pump improves with the initial system temperature, with the amount of water vaporized and with the water remaining in the system. Finally it was also found that lithium chloride salt has higher effect on the performance of the heat pump that of sodium chloride.

Thermochemistry of adducts of some bivalent transition metal bromides with aniline

International Nuclear Information System (INIS)

Dunstan, Pedro Oliver

2006-01-01

The compounds [MBr 2 (an) 2 ] (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II); an=aniline) were synthesized and characterized by melting points, elemental analysis, thermal studies, and electronic and IR spectroscopy. The enthalpies of dissolution of the adducts, metal(II) bromides and aniline in methanol, aqueous 1.2M HCl or 25% (v/v) aqueous 1.2M HCl in methanol were measured. The following thermochemical parameters for the adducts have been determined by thermochemical cycles: the standard enthalpies for the Lewis acid/base reactions (Δ r H o ), the standard enthalpies of formation (Δ f H o ), the standard enthalpies of decomposition (Δ D H o ), the lattice standard enthalpies (Δ M H o ) and the standard enthalpies of the Lewis acid/base reactions in the gaseous phase (Δ r H o (g)). The mean bond dissociation enthalpies of the M(II)-nitrogen bonds (D-bar (M?N) ) and the enthalpies of formation of the adducts from the ions in the gaseous phase: M 2+ (g) +Br - (g) +an (g) ->[MBr 2 (an) 2 ] (g) (Δ fi H o ) have been estimated

The nitrogen cycle: Atmosphere interactions

Science.gov (United States)

Levine, J. S.

1984-01-01

Atmospheric interactions involving the nitrogen species are varied and complex. These interactions include photochemical reactions, initiated by the absorption of solar photons and chemical kinetic reactions, which involve both homogeneous (gas-to-gas reactions) and heterogeneous (gas-to-particle) reactions. Another important atmospheric interaction is the production of nitrogen oxides by atmospheric lightning. The nitrogen cycle strongly couples the biosphere and atmosphere. Many nitrogen species are produced by biogenic processes. Once in the atmosphere nitrogen oxides are photochemically and chemically transformed to nitrates, which are returned to the biosphere via precipitation, dry deposition and aerosols to close the biosphere-atmosphere nitrogen cycle. The sources, sinks and photochemistry/chemistry of the nitrogen species; atmospheric nitrogen species; souces and sinks of nitrous oxide; sources; sinks and photochemistry/chemistry of ammonia; seasonal variation of the vertical distribution of ammonia in the troposphere; surface and atmospheric sources of the nitrogen species, and seasonal variation of ground level ammonia are summarized.

Positron bound states on hydride ions in thermochemically reduced MgO single crystals

International Nuclear Information System (INIS)

Monge, M.A.; Pareja, R.; Gonzalez, R.; Chen, Y.

1996-01-01

Positron-lifetime and Doppler-broadening techniques were used to unambiguously identify positronium hydrides in thermochemically reduced MgO crystals at low temperatures. Positrons trapped at H - ions, forming PsH, yield a lifetime of (640±40) ps, independent of temperature. Complementary evidence for this identification was provided by Doppler-broadening experiments, in which positrons were trapped at H 2- sites at low temperatures. The H 2- ions were formed via H - +e - →H 2- by the capturing of an electron released from Fe + impurity under blue-light stimulation. copyright 1996 The American Physical Society

System efficiency for two-step metal oxide solar thermochemical hydrogen production – Part 2: Impact of gas heat recuperation and separation temperatures

KAUST Repository

Ehrhart, Brian D.

2016-09-22

The solar-to-hydrogen (STH) efficiency is calculated for various operating conditions for a two-step metal oxide solar thermochemical hydrogen production cycle using cerium(IV) oxide. An inert sweep gas was considered as the O2 removal method. Gas and solid heat recuperation effectiveness values were varied between 0 and 100% in order to determine the limits of the effect of these parameters. The temperature at which the inert gas is separated from oxygen for an open-loop and recycled system is varied. The hydrogen and water separation temperature was also varied and the effect on STH efficiency quantified. This study shows that gas heat recuperation is critical for high efficiency cycles, especially at conditions that require high steam and inert gas flowrates. A key area for future study is identified to be the development of ceramic heat exchangers for high temperature gas-gas heat exchange. Solid heat recuperation is more important at lower oxidation temperatures that favor temperature-swing redox processing, and the relative impact of this heat recuperation is muted if the heat can be used elsewhere in the system. A high separation temperature for the recycled inert gas has been shown to be beneficial, especially for cases of lower gas heat recuperation and increased inert gas flowrates. A higher water/hydrogen separation temperature is beneficial for most gas heat recuperation effectiveness values, though the overall impact on optimal system efficiency is relatively small for the values considered. © 2016 Hydrogen Energy Publications LLC.

High-temperature nuclear reactor power plant cycle for hydrogen and electricity production – numerical analysis

Directory of Open Access Journals (Sweden)

Dudek Michał

2016-01-01

Full Text Available High temperature gas-cooled nuclear reactor (called HTR or HTGR for both electricity generation and hydrogen production is analysed. The HTR reactor because of the relatively high temperature of coolant could be combined with a steam or gas turbine, as well as with the system for heat delivery for high-temperature hydrogen production. However, the current development of HTR’s allows us to consider achievable working temperature up to 750°C. Due to this fact, industrial-scale hydrogen production using copper-chlorine (Cu-Cl thermochemical cycle is considered and compared with high-temperature electrolysis. Presented calculations show and confirm the potential of HTR’s as a future solution for hydrogen production without CO2 emission. Furthermore, integration of a hightemperature nuclear reactor with a combined cycle for electricity and hydrogen production may reach very high efficiency and could possibly lead to a significant decrease of hydrogen production costs.

Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

Energy Technology Data Exchange (ETDEWEB)

Schuenemann, V. [University of Luebeck, Institute of Physics (Germany); Jung, C. [Max-Delbrueck-Center for Molecular Medicine (Germany); Lendzian, F. [Technical University, PC 14, Max-Volmer Laboratory for Biophysical Chemistry (Germany); Barra, A.-L. [Grenoble High Magnetic Field Laboratory (France); Teschner, T.; Trautwein, A. X. [University of Luebeck, Institute of Physics (Germany)

2004-12-15

In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

Moessbauer- and EPR-Snapshots of an Enzymatic Reaction: The Cytochrome P450 Reaction Cycle

International Nuclear Information System (INIS)

Schuenemann, V.; Jung, C.; Lendzian, F.; Barra, A.-L.; Teschner, T.; Trautwein, A. X.

2004-01-01

In this communication we present a complimentary Moessbauer- and EPR-study of the time dependance of the reaction of substrate free P450cam with peracetic acid within a time region ranging from 8 ms up to 5 min. An Fe(IV) species as well as a tyrosyl radical residing on the amino acid residue Tyr96 have been identified as reaction intermediates. These species possibly are formed by the reduction of compound I by means of transferring an electron from Tyr 96 to the heme moiety.

Influence of refreshment/activation cycles and temperature rise on the reaction rate of sodium hypochlorite with bovine dentine during ultrasonic activated irrigation.

Science.gov (United States)

Macedo, R G; Verhaagen, B; Wesselink, P R; Versluis, M; van der Sluis, L W M

2014-02-01

To evaluate the effect of multiple refreshment/activation cycles and temperature on the reaction rate of sodium hypochlorite (NaOCl) with bovine dentine during ultrasonic activated irrigation (UAI) under laboratory conditions. The root canal walls of 24 standardized root canals in bovine incisors were exposed to a standardized volume of NaOCl at different temperatures (24 °C and 38 °C) and exposure times (20, 60 and 180 s). The irrigant was refreshed and ultrasonically activated four times for 20 s followed by a 40 s rest interval, with no refreshment and no activation as the controls. The reaction rate was determined by measuring the amount of active chlorine in the NaOCl solution before and after being exposed to dentine during the specific experimental conditions. Calorimetry was used to measure the electrical-to-sonochemical conversion efficiency during ultrasonic activation. Refreshment, activation and exposure time all increased the reaction rate of NaOCl (P reaction rate of NaOCl (P > 0.125). The reaction rate of NaOCl with dentine is enhanced by refreshment, ultrasonic activation and exposure time. Temperature rise of irrigant during ultrasonic activation was not sufficient to alter the reaction rate. © 2013 International Endodontic Journal. Published by John Wiley & Sons Ltd.

Environmental requirements in thermochemical and biochemical conversion of biomass

International Nuclear Information System (INIS)

Frings, R.M.; Mackie, K.L.; Hunter, I.R.

1992-01-01

Many biological and thermochemical processing options exist for the conversion of biomass to fuels. Commercially, these options are assessed in terms of fuel product yield and quality. However, attention must also be paid to the environmental aspects of each technology so that any commercial plant can meet the increasingly stringent environmental legislation in the world today. The environmental aspects of biological conversion (biogasification and bioliquefaction) and thermal conversion (high pressure liquefaction, flash pyrolysis, and gasification) are reviewed. Biological conversion processes are likely to generate waste streams which are more treatable than those from thermal conversion processes but the available data for thermal liquefaction are very limited. Close attention to waste minimisation is recommended and processing options that greatly reduce or eliminate waste streams have been identified. Product upgrading and its effect on wastewater quality also requires attention. Emphasis in further research studies needs to be placed on providing authentic waste streams for environmental assessment. (author)

Characteristics of thermochemical treated EN10090 X50 steel

International Nuclear Information System (INIS)

Schmitz, S.; Graf, K.; Scheid, A.; Moreno, A.

2014-01-01

EN10090 X50 steel is commonly used for engine valves to withstand severe operation conditions involving high temperature and corrosion from fuel and combustion gas. Usually, to enhance wear performance, valves undergo nitriding thermochemical treatment by salt baths. The aim of this work is to produce diffusion layers at least 20μm thick with hardness higher than 700HV by plasma surface treatment with no continuous compounds layer using nitrogen and methane based atmospheres. Samples were characterized by laser Confocal and scanning electron microscopy, X-ray diffraction and Vickers hardness. Salt bath treatment induced formation of undesirable compounds layer at the surface and a diffusion layer thicker than 40μm, with hardness arising 1280HV_0_,_0_1_0. Plasma surface treatment produced diffusion layer thicker than 40μm with no continuous compounds layer and mean hardness varying from 750 to 960HV_0_,_0_1_0. (author)

Blanket materials for fusion reactors: comparisons of thermochemical performance

International Nuclear Information System (INIS)

Johnson, C.E.; Fischer, A.K.; Tetenbaum, M.

1984-01-01

Thermodynamic calculations have been made to predict the thermochemical performance of the fusion reactor breeder materials, Li 2 O, LiAlO 2 , and Li 4 SiO 4 in the temperature range 900 to 1300 0 K and in the oxygen activity range 10 -25 to 10 -5 . Except for a portion of these ranges, the performance of LiAlO 2 is predicted to be better than that of Li 2 O and Li 4 SiO 4 . The protium purge technique for enhancing tritium release is explored for the Li 2 O system; it appears advantageous at higher temperatures but should be used cautiously at lower temperatures. Oxygen activity is an important variable in these systems and must be considered in executing and interpreting measurements on rates of tritium release, the form of released tritium, diffusion of tritiated species and their identities, retention of tritium in the condensed phase, and solubility of hydrogen isotope gases

Thermochemical properties of media for pyrometallurgical nuclear fuel reprocessing

International Nuclear Information System (INIS)

Hosoya, Yuji; Terai, Takayuki

1998-01-01

Molten chloride/cadmium system is considered to be applied to a solvent in pyrochemical reprocessing of spent nuclear fuel. In this work, phase diagrams for molten chloride systems were constructed, using NdCl 3 as an imitative substance in place of UCl 3 or PuCl 3 . Hastelloy-X (Ni/Cr21/Fe18/Mo9/W) was examined as a structural material for the corrosion-resistance against molten chloride baths containing NdCl 3 . The process of corrosion was thermochemically discussed and the form of the corrosion was illustrated. Rutherford backscattering spectroscopy was successfully applied to determine the elemental distribution profile of specimens tested on the compatibility with molten chloride mixture at elevated temperature. Ferritic steel was also examined as another candidate material for the compatibility with molten cadmium covered with LiCl-KCl eutectic salt. Variation of near-surface composition was observed by comparing the results of Rutherford backscattering spectroscopy obtained before and after the dipping. (author)

Study of water nature in some crystallohydrates of pentasubstituted alkali metal salts of borotungstic acid using thermochemical method

International Nuclear Information System (INIS)

Kosmodem'yanskaya, G.V.; Sadykova, M.M.; Spitsyn, V.I.

1977-01-01

Kinetics of the dehydration process has been studied and heat of dehydration has been determined for salts 2.5Li 2 O x 0.5B 2 O 3 x 12.0WO 3 x 28.5H 2 O; 2.5Na 2 Ox0.5B 2 O 3 x 12.0WO 3 x 17.5H 2 O; 2.5K 2 O x 0.5B 2 O 3 x12.0WO 3 x 16.5H 2 O; 2.5Cs 2 O x 0.5B 2 O 3 x 12.0WO 3 x6.7H 2 O. Dehydration has been conducted in vacuum at 25-50 deg C. The study of the dehydration process has been performed thermochemically in a differential calorimeter. It has been shown that heat of dehydration depends on the nature of the cation. Lithium salt with a cation of a small radius has the highest heat of dehydration (6.4+-0.2 kcal/mol H 2 O). Cesium salt is dehydrated almost completely. A considerable part of water in crystallohydrates has a salting character. Kinetics of the dehydration process is described by the equation of the monomolecular reaction

Interest of thermochemical data bases linked to complex equilibria calculation codes for practical applications

International Nuclear Information System (INIS)

Cenerino, G.; Marbeuf, A.; Vahlas, C.

1992-01-01

Since 1974, Thermodata has been working on developing an Integrated Information System in Inorganic Chemistry. A major effort was carried on the thermochemical data assessment of both pure substances and multicomponent solution phases. The available data bases are connected to powerful calculation codes (GEMINI = Gibbs Energy Minimizer), which allow to determine the thermodynamical equilibrium state in multicomponent systems. The high interest of such an approach is illustrated by recent applications in as various fields as semi-conductors, chemical vapor deposition, hard alloys and nuclear safety. (author). 26 refs., 6 figs

CO/sub 2/ carbon cycle and climate interactions

Energy Technology Data Exchange (ETDEWEB)

Grassl, H; Maier-Reimer, E; Degens, E T; Kempe, S; Spitzy, A

1984-03-01

Past and expected emissions of anthropogenic CO/sub 2/ stimulate carbon cycle and climate research. Prognoses of future CO/sub 2/ levels depend on energy scenarios and on the reaction of the biosphere and hydrosphere to elevated atmospheric CO/sub 2/ concentrations. The reaction of the reservoirs vegetation, freshwater and oceans to disturbances of the carbon cycle is reviewed. For the oceans first results of a simple carbon cycle model implanted in a three-dimensional general circulation model are presented. This model allows experiments not possible with previous box models.

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

Science.gov (United States)

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.

Survey and Down-Selection of Acid Gas Removal Systems for the Thermochemical Conversion of Biomass to Ethanol with a Detailed Analysis of an MDEA System

Energy Technology Data Exchange (ETDEWEB)

Nexant, Inc., San Francisco, California

2011-05-01

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 chosen for detailed study because of the available resources.

Fuels production by the thermochemical transformation of the biomass; La production de carburants par transformation thermochimique de la biomasse

Energy Technology Data Exchange (ETDEWEB)

Claudet, G. [CEA, 75 - Paris (France)

2005-07-01

The biomass is a local and renewable energy source, presenting many advantages. This paper proposes to examine the biomass potential in France, the energy valorization channels (thermochemical chains of thermolysis and gasification) with a special interest for the hydrogen production and the research programs oriented towards the agriculture and the forest. (A.L.B.)

Cell cycle arrest induced by radiation

International Nuclear Information System (INIS)

Okaichi, Yasuo; Matsumoto, Hideki; Ohnishi, Takeo

1994-01-01

It is known that various chemical reactions, such as cell cycle arrest, DNA repair and cell killing, can occur within the cells when exposed to ionizing radiation and ultraviolet radiation. Thus protein dynamics involved in such chemical reactions has received considerable attention. In this article, cell cycle regulation is first discussed in terms of the G2/M-phase and the G1/S-phase. Then, radiation-induced cell cycle arrest is reviewed. Cell cycle regulation mechanism involved in the G2 arrest, which is well known to occur when exposed to radiation, has recently been investigated using yeasts. In addition, recent study has yielded a noticeable finding that the G1 arrest can occur with intracellular accumulation of p53 product following ionization radiation. p53 is also shown to play an extremely important role in both DNA repair and cell killing due to DNA damage. Studies on the role of genes in protein groups induced by radiation will hold promise for the elucidation of cell cycle mechanism. (N.K.) 57 refs

Thermochemical cycles for the heat and cold long-range transport. Final report of the PRI 9.2 Cold transport. Annual report of the PR 2-8; Cycles thermochimiques pour le transport de chaleur et de froid a longue distance. Rapport final du PRI 9.2. Transport de froid. Rapport annuel du PR 2-8

Energy Technology Data Exchange (ETDEWEB)

Luo, L.; Tondeur, D. [Laboratoire des Sciences du Genie Chimique (LSGC), 54 - Nancy (France); Mazet, N.; Neveu, P.; Stitou, D.; Spinner, B. [Institut de Science et de Genie des Materiaux et Procedes (IMP), 66 - Perpignan (France)

2004-07-01

This PRI deals with the use of thermochemical processes, based on solid-gas reversible transformation, to transfer heat of cold at long-range distance (> 10 km), in order to enhance the energy efficiency. Four main aspects have been studied to confirm the process feasibility: the process identification and the operating conditions, the selection of compatible reagents, the design of an auto-thermal reactor and the gas transport impact on the global performances. (A.L.B.)

Effect of NiO/SiO2 on thermo-chemical conversion of waste cooking oil to hydrocarbons

Directory of Open Access Journals (Sweden)

J. Sani

2017-05-01

Full Text Available Increase in organic waste generation, dwindling nature of global oil reserves coupled with environmental challenges caused by waste oil disposal and burning of fossil fuels necessitated the need for alternative energy resources. Waste cooking oil obtained from the frying fish outlet was analyzed for its physicochemical properties using ASTM D-975 methods. Acid and Iodine values of the oil were 30.43 ± 0.32 mgKOH/g and 57.08 ± 0.43 mgI2/100 g respectively. Thermo-chemical conversion of the oil using NiO/SiO2 at different reaction conditions (pressure, temperature, and catalyst concentration at a residence time of 3 h yielded 33.63% hydrocarbons. Hydro-catalytic pyrolysis of waste cooking oil at 400 °C, H2 pressure of 15 bars, and catalyst to oil ratio of 0.25 g/100 cm3 resulted in highest hydrocarbon yield (41.98%. The fuel properties of the product were: cetane number (71.16, high heating value (41.43 MJ/kg, kinematic viscosity (2.01 mm2/s, density (0.94 g/ml, saponification value (185.1 ± 3.96 mgKOH/g, and iodine value (20.57 ± 0.20 I2/100 g respectively. These results show that the NiO/SiO2 could be a suitable catalyst for conversion of waste vegetable oil to hydrocarbons. Keywords: Energy, Chemical engineering

NUMBER OF SUCCESSIVE CYCLES NECESSARY TO ACHIEVE STABILITY OF SELECTED GROUND REACTION FORCE VARIABLES DURING CONTINUOUS JUMPING

Directory of Open Access Journals (Sweden)

Jasmes M.W. Brownjohn

2009-12-01

Full Text Available Because of inherent variability in all human cyclical movements, such as walking, running and jumping, data collected across a single cycle might be atypical and potentially unable to represent an individual's generalized performance. The study described here was designed to determine the number of successive cycles due to continuous, repetitive countermovement jumping which a test subject should perform in a single experimental session to achieve stability of the mean of the corresponding continuously measured ground reaction force (GRF variables. Seven vertical GRF variables (period of jumping cycle, duration of contact phase, peak force amplitude and its timing, average rate of force development, average rate of force relaxation and impulse were extracted on the cycle-by-cycle basis from vertical jumping force time histories generated by twelve participants who were jumping in response to regular electronic metronome beats in the range 2-2.8 Hz. Stability of the selected GRF variables across successive jumping cycles was examined for three jumping rates (2, 2.4 and 2.8 Hz using two statistical methods: intra-class correlation (ICC analysis and segmental averaging technique (SAT. Results of the ICC analysis indicated that an average of four successive cycles (mean 4.5 ± 2.7 for 2 Hz; 3.9 ± 2.6 for 2.4 Hz; 3.3 ± 2.7 for 2.8 Hz were necessary to achieve maximum ICC values. Except for jumping period, maximum ICC values took values from 0.592 to 0.991 and all were significantly (p < 0.05 different from zero. Results of the SAT revealed that an average of ten successive cycles (mean 10.5 ± 3.5 for 2 Hz; 9.2 ± 3.8 for 2.4 Hz; 9.0 ± 3.9 for 2.8 Hz were necessary to achieve stability of the selected parameters using criteria previously reported in the literature. Using 10 reference trials, the SAT required standard deviation criterion values of 0.49, 0.41 and 0.55 for 2 Hz, 2.4 Hz and 2.8 Hz jumping rates, respectively, in order to approximate

Free energies for degradation reactions of 1,2,3-trichloropropane from ab initio electronic structure theory.

Science.gov (United States)

Bylaska, Eric J; Glaesemann, Kurt R; Felmy, Andrew R; Vasiliu, Monica; Dixon, David A; Tratnyek, Paul G

2010-11-25

Electronic structure methods were used to calculate the gas and aqueous phase reaction energies for reductive dechlorination (i.e., hydrogenolysis), reductive β-elimination, dehydrochlorination, and nucleophilic substitution by OH− of 1,2,3-trichloropropane. The thermochemical properties ΔH(f)°(298.15 K), S°(298.15 K, 1 bar), and ΔG(S)(298.15 K, 1 bar) were calculated by using ab initio electronic structure calculations, isodesmic reactions schemes, gas-phase entropy estimates, and continuum solvation models for 1,2,3-trichloropropane and several likely degradation products: CH3−CHCl−CH2Cl, CH2Cl−CH2−CH2Cl, C•H2−CHCl−CH2Cl, CH2Cl−C•H−CH2Cl, CH2═CCl−CH2Cl, cis-CHCl═CH−CH2Cl, trans-CHCl═CH−CH2Cl, CH2═CH−CH2Cl, CH2Cl−CHCl−CH2OH, CH2Cl−CHOH−CH2Cl, CH2═CCl−CH2OH, CH2═COH−CH2Cl, cis-CHOH═CH−CH2Cl, trans-CHOH═CH−CH2Cl, CH(═O)−CH2−CH2Cl, and CH3−C(═O)−CH2Cl. On the basis of these thermochemical estimates, together with a Fe(II)/Fe(III) chemical equilibrium model for natural reducing environments, all of the reactions studied were predicted to be very favorable in the standard state and under a wide range of pH conditions. The most favorable reaction was reductive β-elimination (ΔG(rxn)° ≈ −32 kcal/mol), followed closely by reductive dechlorination (ΔG(rxn)° ≈ −27 kcal/mol), dehydrochlorination (ΔG(rxn)° ≈ −27 kcal/mol), and nucleophilic substitution by OH− (ΔG(rxn)° ≈ −25 kcal/mol). For both reduction reactions studied, it was found that the first electron-transfer step, yielding the intermediate C•H2−CHCl−CH2Cl and the CH2Cl−C•H−CH2Cl species, was not favorable in the standard state (ΔG(rxn)° ≈ +15 kcal/mol) and was predicted to occur only at relatively high pH values. This result suggests that reduction by natural attenuation is unlikely.

Benchmark Study of the Structural and Thermochemical Properties of a Dihydroazulene/Vinylheptafulvene Photoswitch

DEFF Research Database (Denmark)

Koerstz, Mads; Elm, Jonas; Mikkelsen, Kurt Valentin

2017-01-01

We investigate the performance of four different density functional theory (DFT) functionals (M06-2X, ωB97X-D, PBE0, and B3LYP-D3BJ) for calculating the structural and thermochemical properties of the dihydroazulene/vinylheptafulvene photoswitch (DHA/VHF). We find that all the tested DFT......, indicating that the largest source of error when calculating storage free energies originates from errors in the calculated single point energies. It was found that ωB97X-D and M06-2X performed decently for predicting storage energies. While B3LYP-D3BJ and PBE0 generally underestimated the storage energy...

Estimation of the reaction efficiency in polymerase chain reaction

NARCIS (Netherlands)

Lalam, N.

2006-01-01

Polymerase chain reaction (PCR) is largely used in molecular biology for increasing the copy number of a specific DNA fragment. The succession of 20 replication cycles makes it possible to multiply the quantity of the fragment of interest by a factor of 1 million. The PCR technique has

Why we haven't died out yet: changes in women's mimic reactions to visual erotic stimuli during their menstrual cycles.

Science.gov (United States)

Mass, Reinhard; Hölldorfer, Marion; Moll, Bettina; Bauer, Renate; Wolf, Karsten

2009-02-01

From an evolutionary point of view, female sexual desire contributes greatly to the success of reproduction by coordinating sexual behavior. It is known that female sexual desire fluctuates with the menstrual cycle. However, little is known about the role of basic emotions during menstrual cycle. We designed a facial EMG study to investigate facial expressions of joy during the menstrual cycle. 35 healthy women underwent 2 EMG sessions (T1 and T2). T1 took place in the follicular phase, T2 in the luteal phase. IAPS pictures of nude men (erotic stimuli) or of animals (control stimuli) were presented at both sessions. The activity of musculus zygomaticus major (responsible for expressing joy) was measured. We tested the hypothesis that zygomaticus activity is more pronounced in the follicular phase than in the luteal phase. The main result was that during the follicular phase, significantly more zygomaticus reactions were observed than during the luteal phase. This effect was restricted only to erotic stimuli. We concluded that an increased positive emotional responsiveness to erotic stimuli during the follicular phase is an important precondition for the probability of sexual activity during the conceptive days and thus for the success of reproduction.

Thermodynamic analysis and experimental study on the chlorination of uranium oxide by gas-solid reaction

International Nuclear Information System (INIS)

Shin, Y.J.; Kim, I.S.; Shin, H.S.; Ro, S.G.; Park, H.S.

1998-01-01

In order to determine the operating condition of an uranium chlorination process with U 3 O 8 -C-Cl 2 system, the experimental conditions have been evaluated preliminarily by the thermochemical analysis and experimentally confirmed in this study. The dry-type chlorination of U 3 O 8 occurs as irreversible and exothermic reaction and produces many kinds of chloride compounds such as UCl 3 , UCl 4 , UCl 5 , and UCl 6 in the air and humidity controlled argon environment. Taking account of Gibbs free energy and vapor pressure for various chloride compounds, the proper temperature range of chlorination appears to be 863 to 953 K in aspects of increasing reaction rate and the yield of nonvolatile product. In the course of the experimental confirmation the powder of U 3 O 8 is perfectly converted into uranium chlorides within 4 hours above 863 K, and then the maximum fraction of uranium chloride remaining in the reactor is about 30% of total conversion mass. (author)

Summarized achievement report on the Sunshine Project in fiscal 1979. Hydrogen energy; 1979 nendo sunshine keikaku seika hokokusho gaiyoshu. Suiso energy

Energy Technology Data Exchange (ETDEWEB)

NONE

1980-04-01

This paper summarizes the achievement report on the Sunshine Project in fiscal 1979 for hydrogen energy research. In hydrogen manufacturing technologies, the paper describes improvement in membrane performance and discussions on electrode materials in high temperature and pressure electrolysis. In the thermo-chemical method, hydrolysis of iron bromide (II) in the iron system cycle was compared to three kinds of reaction patterns corresponding to phase change, and evaluation was given as the hydrogen generating reaction. In the iodine system the first stage oxidation and reduction reaction of MgO-I{sub 2} was subjected to a continued experiment by using a batch autoclave. Discussions were continued on device materials for the iodine cycle. In the light irradiation electrolytic method for the mixed cycle, the light intensity was experimented at a force 12 times greater than that of the solar beam, and a reaction rate of 80% was achieved. Raising the temperature causes the reaction rate to decline, but it can be supplemented by raising the light intensity. A heat diffusion column was found effective in HI decomposition (hydrogen acquisition). For hydrogen transportation and storage, researches are continued on metal hydrides. In hydrogen utilization technologies, combustion, fuel cells (using high temperature solid and alkaline aqueous solution electrolytes), and hydrogen engines are studied. This paper also describes studies on hydrogen safety assuring measures and energy systems. (NEDO)

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

Science.gov (United States)

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.

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

Science.gov (United States)

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.

PWR fuel physico chemistry. Improvements of the Sage code to compute thermochemical balance in PWR fuel

International Nuclear Information System (INIS)

Garcia, P.; Baron, D.; Piron, J.P.

1993-02-01

A physicochemical survey of high burnup fuel has been undertaken in the context of a 3-party action (CEA Cadarache - EDF/DER - FRAMATOME). One of the tasks involved consists in adapting the SAGE code for assessment of the thermochemical equilibria of fission products in solution in the fuel matrix. This paper describes the first stage of this task. Even if other improvements are planned, the oxid oxygen potentials are yet properly reproduced for the simulated burnup. (authors). 63 figs., 4 tabs., 41 refs

Thermochemical transformations of anthracene oil

Energy Technology Data Exchange (ETDEWEB)

Belkina, T.V.; Privalov, V.E.; Stepanenko, M.A.

1979-01-01

The basic technological step in electrode pitch production is the thermal processing of the original pitch, combined in some cases with air treatment. The thermal process of electrode pitch production is outstandingly simple and economical, but offers little scope for regulating the product quality. When the coal tar regulating the product quality has been highly pyrolyzed, it becomes difficult to produce a medium electrode pitch in conformity with GOST 10200-73 as regards its content of substances insoluble in quinoline (..cap alpha../sub 1/-fraction). It is particularly difficult to make ptich with a softening point of 85 to 90/sup 0/C from highly pyrolyzed coal tar, since this involves a prolonged treatment which increases the ..cap alpha../sub 1/-fraction content. These difficulties, associated with persistent consumer demand for higher electrode pitch quality, have greatly activated the search for new methods of making electrode pitch. A survey of the Soviet and foreign literature shows that the investigations now in progress relate both to methods of developing new production techniques and to methods of adjusting the initial feedstock composition by the addition of high-boiling coal-tar fractions, pitch distillates, highly aromatized petroleum refinery products and so on. As a result of experiments it was found that: (1) When anthracene oil is heated, its contents of condensation products (..cap alpha../sub 1/- and ..cap alpha..-fractions) increase quite slowly compared with pitch; consequently the electrode pitch production process is prolonged by mixing the two feedstock materials. (2) When the anthracene oil is heat treated first, condensation products form and accumulate in it and its thermochemical transformation activity is enhanced. (3) The use of heat-treated anthracene oil will clearly intensify the electrode pitch production process and raise the product quality.

Study of thermochemically reduced and electron-irradiated LiNbO3 single crystals by positron annihilation and optical absorption measurements

International Nuclear Information System (INIS)

Pareja, R.; Gonzalez, R.; Pedrosa, M.A.

1984-01-01

Irradiation of LiNbO 3 single crystals using Van de Graaff electrons with an energy of 1.5 MeV introduces an optical absorption band similar to that observed in thermochemically reduced samples. As-grown, reduced, or irradiated crystals show single-component positron lifetime spectra with an average decay time of 234 ps. (author)