Composite mixed conductors comprising one electronic conducting phase, and one ionic conducting phase (MIECs) have been developed in this work. Such MIECs have applications in generating and separating hydrogen from hydrocarbon fuels at high process rates and high purities. The ionic conducting phase comprises of rare-earth doped ceria and the electronic conducting phase of rare-earth doped strontium titanate. These compositions are ideally suited for the hydrogen separation application. In the process studied in this project, steam at high temperatures is fed to one side of the MIEC membrane and hydrocarbon fuel or reformed hydrocarbon fuel to the other side of the membrane. Oxygen is transported from the steam side to the fuel side down the electrochemical potential gradient thereby enriching the steam side flow in hydrogen. The remnant water vapor can then be condensed to obtain high purity hydrogen. In this work we have shown that two-phase MIECs comprising rare-earth ceria as the ionic conductor and doped-strontium titanate as the electronic conductor are stable in the operating environment of the MIEC. Further, no adverse reaction products are formed when these phases are in contact at elevated temperatures. The composite MIECs have been characterized using a transient electrical conductivity relaxation technique …

The modeling of coupled thermal, hydrological, and chemical (THC) processes in geothermal systems is complicated by reservoir conditions such as high temperatures, elevated pressures and sometimes the high salinity of the formation fluid. Coupled THC models have been developed and applied to the study of enhanced geothermal systems (EGS) to forecast the long-term evolution of reservoir properties and to determine how fluid circulation within a fractured reservoir can modify its rock properties. In this study, two simulators, FRACHEM and TOUGHREACT, specifically developed to investigate EGS, were applied to model the same geothermal reservoir and to forecast reservoir evolution using their respective thermodynamic and kinetic input data. First, we report the specifics of each of these two codes regarding the calculation of activity coefficients, equilibrium constants and mineral reaction rates. Comparisons of simulation results are then made for a Soultz-type geothermal fluid (ionic strength {approx}1.8 molal), with a recent (unreleased) version of TOUGHREACT using either an extended Debye-Hueckel or Pitzer model for calculating activity coefficients, and FRACHEM using the Pitzer model as well. Despite somewhat different calculation approaches and methodologies, we observe a reasonably good agreement for most of the investigated factors. Differences in the calculation schemes typically produce less difference …

Solid-state sensors were developed for coal combustion control and the understanding of sensing mechanisms was advanced. Several semiconducting metal oxides (p-type and n-type) were used to fabricate sensor electrodes. The adsorption/desorption characteristics and catalytic activities of these materials were measured with Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction (TPR) experiments. The sensitivity, selectivity, and response time of these sensors were measured for steps of NO, NO{sub 2}, CO, CO{sub 2}, O{sub 2}, and H{sub 2}O vapor in simple N{sub 2}-balanced and multi-component, simulated combustion-exhaust streams. The role of electrode microstructure and fabrication parameters on sensing performance was investigated. Proof for the proposed sensing mechanism, Differential Electrode Equilibria, was demonstrated by relating the sensing behavior (sensitivities and cross-sensitivities) of the various electrode materials to their gas adsorption/desorption behaviors and catalytic activities. A multifunctional sensor array consisting of three sensing electrodes and an integrated heater and temperature sensors was fabricated with tape-casting and screen-printing and its NO{sub x} sensing performance was measured. The multifunctional sensor demonstrated it was possible to measure NO{sub 2} independent of NO by locally heating one of the sensing electrodes. The sensor technology was licensed to Fuel FX International, Inc. Fuel FX has obtained investor funding and …

Many metal extraction operations, such as leaching of copper, leaching of precious metals, and reduction of metal oxides to metal in high-temperature furnaces, require agglomeration of ore to ensure that reactive liquids or gases are evenly distributed throughout the ore being processed. Agglomeration of ore into coarse, porous masses achieves this even distribution of fluids by preventing fine particles from migrating and clogging the spaces and channels between the larger ore particles. Binders are critically necessary to produce agglomerates that will not break down during processing. However, for many important metal extraction processes there are no binders known that will work satisfactorily. Primary examples of this are copper heap leaching, where there are no binders that will work in the acidic environment encountered in this process, and advanced ironmaking processes, where binders must function satisfactorily over an extraordinarily large range of temperatures (from room temperature up to over 1200 C). As a result, operators of many facilities see a large loss of process efficiency due to their inability to take advantage of agglomeration. The large quantities of ore that must be handled in metal extraction processes also means that the binder must be inexpensive and useful at low dosages to …

This past year has seen both challenges and fantastic new opportunities for the user community at the NSLS. The fantastic new opportunities are clear and abundant. We now have a five-year strategic plan for new development and continued operation of the NSLS. The NSLS continues to be an extremely productive facility, and the UEC is delighted at how NSLS Chair Chi-Chang Kao has consulted widely within the user community to develop a five-year plan for strategic upgrades and continued operation of the facility. The NSLS-II project, led by Associate Lab Director Steve Dierker, has done very well in its Department of Energy (DOE) reviews and will hopefully soon receive Critical Decision-1 (CD-1) approval, which in DOE lingo gives a go-ahead to launch the detailed design of the facility. We also held the first joint user meeting between the NSLS and Brookhaven's Center for Functional Nanomaterials (CFN), for which the building is near completion. The joint user meeting is an important step toward the close collaboration of the two facilities. The CFN, led by Emilio Mendez, promises to provide capabilities and research foci that are complementary to those at the NSLS. Together, all of these developments give a clear path to …

Biennial report of the Office of Rural Community Affairs describing goals, activities, and accomplishments during fiscal year 2006.

The chemistry of sol-gel derived silica and refractive metal oxide has been systematically studied. Sol-gel processes have been developed for preparing porous silica and semiconductor metal oxide materials. Micelle/reversed micelle techniques have been developed for preparing nanometer sized semiconductor metal oxides and noble metal particles. Techniques for doping metal ions, metal oxides and nanosized metal particles into porous sol-gel material have also been developed. Optical properties of sol-gel derived materials in ambient and high temperature gases have been studied by using fiber optic spectroscopic techniques, such as fiber optic ultraviolet/visible absorption spectrometry, fiber optic near infrared absorption spectrometry and fiber optic fluorescence spectrometry. Fiber optic spectrometric techniques have been developed for investigating the optical properties of these sol-gel derived materials prepared as porous optical fibers or as coatings on the surface of silica optical fibers. Optical and electron microscopic techniques have been used to observe the microstructure, such as pore size, pore shape, sensing agent distribution, of sol-gel derived material, as well as the size and morphology of nanometer metal particle doped in sol-gel derived porous silica, the nature of coating of sol-gel derived materials on silica optical fiber surface. In addition, the chemical reactions of metal ion, nanostructured semiconductor …

Ti doping on La{sub 1-x}Sr{sub x}FeO{sub 3-{delta}} (LSF) tends to increase the oxygen equilibration kinetics of LSF in lower oxygen activity environment because of the high valence state of Ti. However, the addition of Ti decreases the total conductivity because the acceptor ([Sr{prime}{sub La}]) is compensated by the donor ([Ti{sub Fe}{sup {sm_bullet}}]) which decreases the carrier concentration. The properties of La{sub 0.2}Sr{sub 0.8}Fe{sub 1-x}Ti{sub x}O{sub 3-{delta}} (LSFT, x = 0.45) have been experimentally and theoretically investigated to elucidate (1) the dependence of oxygen occupancy and electrochemical properties on temperature and oxygen activity by thermogravimetric analysis (TGA) and (2) the electrical conductivity and carrier concentration by Seebeck coefficient and electrical measurements. In the present study, dual phase (La{sub 0.2}Sr{sub 0.8}Fe{sub 0.6}Ti{sub 0.4}O{sub 3-{delta}}/Ce{sub 0.9}Gd{sub 0.1}O{sub 2-{delta}}) membranes have been evaluated for structural properties such as hardness, fracture toughness and flexural strength. The effect of high temperature and slightly reducing atmosphere on the structural properties of the membranes was studied. The flexural strength of the membrane decreases upon exposure to slightly reducing conditions at 1000 C. The as-received and post-fractured membranes were characterized using XRD, SEM and TG-DTA to understand the fracture mechanisms. Changes in structural properties of the composite were sought …

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In the early/mid 1990’s Prof. Alvin Radkowsky, former chief scientist of the U.S. Naval Reactors program, proposed an alternate fuel concept employing thorium-based fuel for use in existing/next generation pressurized water reactors (PWRs). The concept was based on the use of a 'seed-blanket-unit' (SBU) that was a one-for-one replacement for a standard PWR assembly with a uranium-based central 'driver' zone, surrounded by a 'blanket' zone containing uranium and thorium. Therefore, the SBU could be retrofit without significant modifications into existing/next generation PWRs. The objective was to improve the proliferation and waste characteristics of the current once-through fuel cycle. The objective of a series of projects funded by the Initiatives for Proliferation Prevention program of the U.S. Department of Energy (DOE-IPP) - BNL-T2-0074,a,b-RU 'Radkowsky Thorium Fuel (RTF) Concept' - was to explore the characteristics and potential of this concept. The work was performed under several BNL CRADAs (BNL-C-96-02 and BNL-C-98-15) with the Radkowsky Thorium Power Corp./Thorium Power Inc. and utilized the technical and experimental capabilities in the Former Soviet Union (FSU) to explore the potential of this concept for implementation in Russian pressurized water reactors (VVERs), and where possible, also generate data that could be used for design and licensing of …

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Adoption of heat pump water heating technology for commercial hot water could save up to 0.4 quads of energy and 5 million metric tons of CO2 production annually in North America, but industry perception is that this technology does not offer adequate performance or reliability and comes at too high of a cost. Development and demonstration of a CO2 heat pump water heater is proposed to reduce these barriers to adoption. Three major themes are addressed: market analysis to understand barriers to adoption, use of advanced reliability models to design optimum qualification test plans, and field testing of two phases of water heater prototypes. Market experts claim that beyond good performance, market adoption requires 'drop and forget' system reliability and a six month payback of first costs. Performance, reliability and cost targets are determined and reliability models are developed to evaluate the minimum testing required to meet reliability targets. Three phase 1 prototypes are designed and installed in the field. Based on results from these trials a product specification is developed and a second phase of five field trial units are built and installed. These eight units accumulate 11 unit-years of service including 15,650 hours and 25,242 cycles of compressor …

Nitric oxide (NO) and nitrogen dioxide (NO2) generated by internal combustion (IC) engines are implicated in adverse environmental and health effects. Even though lean-burn natural gas engines have traditionally emitted lower oxides of nitrogen (NOx) emissions compared to their diesel counterparts, natural gas engines are being further challenged to reduce NOx emissions to 0.1 g/bhp-hr. The Selective NOx Recirculation (SNR) approach for NOx reduction involves cooling the engine exhaust gas and then adsorbing the NOx from the exhaust stream, followed by the periodic desorption of NOx. By sending the desorbed NOx back into the intake and through the engine, a percentage of the NOx can be decomposed during the combustion process. SNR technology has the support of the Department of Energy (DOE), under the Advanced Reciprocating Engine Systems (ARES) program to reduce NOx emissions to under 0.1 g/bhp-hr from stationary natural gas engines by 2010. The NO decomposition phenomenon was studied using two Cummins L10G natural gas fueled spark-ignited (SI) engines in three experimental campaigns. It was observed that the air/fuel ratio ({lambda}), injected NO quantity, added exhaust gas recirculation (EGR) percentage, and engine operating points affected NOx decomposition rates within the engine. Chemical kinetic model predictions using the software …

A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of iron catalyst particles and the formation of ultra-fine particles.

The following report details the results under the DOE SECA program for the period July 2006 through December 2006. Developments pertain to the development of a 3 to 5 kW Solid Oxide Fuel Cell power system for a range of fuels and applications. This report details technical results of the work performed under the following tasks for the SOFC Power System: Task 1 SOFC System Development; Task 2 Solid Oxide Fuel Cell Stack Developments; Task 3 Reformer Developments; Task 4 Development of Balance of Plant Components; Task 5 Project Management; and Task 6 System Modeling & Cell Evaluation for High Efficiency Coal-Based Solid Oxide Fuel Cell Gas Turbine Hybrid System.

This project Final Report is submitted to the U.S. Department of Energy (DOE) as part of Cooperative Agreement DE-FC26-03NT41987, 'Sorbent Injection for Small ESP Mercury Control in Low Sulfur Eastern Bituminous Coal Flue Gas.' Sorbent injection technology is targeted as the primary mercury control process on plants burning low/medium sulfur bituminous coals equipped with ESP and ESP/FGD systems. About 70% of the ESPs used in the utility industry have SCAs less than 300 ft2/1000 acfm. Prior to this test program, previous sorbent injection tests had focused on large-SCA ESPs. This DOE-NETL program was designed to generate data to evaluate the performance and economic feasibility of sorbent injection for mercury control at power plants that fire bituminous coal and are configured with small-sized electrostatic precipitators and/or an ESP-flue gas desulfurization (FGD) configuration. EPRI and Southern Company were co-funders for the test program. Southern Company and Reliant Energy provided host sites for testing and technical input to the project. URS Group was the prime contractor to NETL. ADA-ES and Apogee Scientific Inc. were sub-contractors to URS and was responsible for all aspects of the sorbent injection systems design, installation and operation at the different host sites. Full-scale sorbent injection for mercury control …

1 Overview of Results and their Significance Ceramic perovskite-like oxides with the general formula (A. A0. ...)(B. B0. ...)O3and titanium-based oxides are of great technological interest because of their large piezoelectric and dielectric response characteristics.[1] In doped and nanoengineered forms, titantium dioxide finds increasing application as an organic and hydrolytic photocatalyst. The binary main-group-metal nitride compounds have undergone recent advancements of in-situ heating technology in diamond anvil cells leading to a burst of experimental and theoretical interest. In our DOE proposal, we discussed our unique theoretical approach which applies ab initio electronic calculations in conjunction with systematic group-theoretical analysis of lattice distortions to study two representative phase transitions in ceramic materials: (1) displacive phase transitions in primarily titanium-based perovskite-like oxide ceramics, and (2) reconstructive phase transitions in main-group nitride ceramics. A sub area which we have explored in depth is doped titanium dioxide electrical/optical properties.

The project developed, built, and tested three apparatuses for studying different interactions of carbon dioxide with geologic materials. In Year 1, an online instrument was constructed by coupling a high-pressure carbon dioxide extraction system with a flame ionization detector that can yield a real-time profile and quantitative measurements of hydrocarbons removed from materials such as coal and petroleum reservoir rock. In Years 2 and 3, one instrument was built to measure the excess sorption of carbon dioxide in geologic materials such as coal and showed that measurable uptake of carbon dioxide into the coal matrix is rapid. The final apparatus was built to expose geologic materials to carbon dioxide for long periods of time (weeks to months) under the range of pressures and temperatures relevant to carbon dioxide sequestration. The apparatus allows as many as twenty gram-sized samples of geologic materials to be exposed simultaneously and can also include exposures with geologic brines. The system was used to demonstrate complete conversion of magnesium silicate to magnesium carbonate in less than 4 weeks when exposed to clean water or brine, compared to no measurable conversion of dry magnesium carbonate.

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