The consumption of petroleum by the transportation sector in the United States is roughly equivalent to petroleum imports into the country, which have totaled over 12 million barrels a day every year since 2004. This reliance on foreign oil is a strategic vulnerability for the economy and national security. Further, the effect of unmitigated CO{sub 2} releases on the global climate is a growing concern both here and abroad. Independence from problematic oil producers can be achieved to a great degree through the utilization of non-conventional hydrocarbon resources such as coal, oil-shale and tarsands. However, tapping into and converting these resources into liquid fuels exacerbates green house gas (GHG) emissions as they are carbon rich, but hydrogen deficient. Revolutionary thinking about energy and fuels must be adopted. We must recognize that hydrocarbon fuels are ideal energy carriers, but not primary energy sources. The energy stored in a chemical fuel is released for utilization by oxidation. In the case of hydrogen fuel the chemical product is water; in the case of a hydrocarbon fuel, water and carbon dioxide are produced. The hydrogen economy envisions a cycle in which H{sub 2}O is re-energized by splitting water into H{sub 2} and O{sub 2}, by electrolysis for example. We envision a hydrocarbon analogy in which both carbon dioxide and water are re-energized through the application of a persistent energy source (e.g. solar or nuclear). This is of course essentially what the process of photosynthesis accomplishes, albeit with a relatively low sunlight-to-hydrocarbon efficiency. The goal of this project then was the creation of a direct and efficient process for the solar or nuclear driven thermochemical conversion of CO{sub 2} to CO (and O{sub 2}), one of the basic building blocks of synthetic fuels. This process would potentially provide the basis for an alternate hydrocarbon economy that is carbon neutral, provides a pathway to energy independence, and is compatible with much of the existing fuel infrastructure.
Molecular simulations are used to assess the ability of metal-organic framework (MOF) materials to store and separate noble gases. Specifically, grand canonical Monte Carlo simulation techniques are used to predict noble gas adsorption isotherms at room temperature. Experimental trends of noble gas inflation curves of a Zn-based material (IRMOF-1) are matched by the simulation results. The simulations also predict that IRMOF-1 selectively adsorbs Xe atoms in Xe/Kr and Xe/Ar mixtures at total feed gas pressures of 1 bar (14.7 psia) and 10 bar (147 psia). Finally, simulations of a copper-based MOF (Cu-BTC) predict this material's ability to selectively adsorb Xe and Kr atoms when present in trace amounts in atmospheric air samples. These preliminary results suggest that Cu-BTC may be an ideal candidate for the pre-concentration of noble gases from air samples. Additional simulations and experiments are needed to determine the saturation limit of Cu-BTC for xenon, and whether any krypton atoms would remain in the Cu-BTC pores upon saturation.
Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximity and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.
We have synthesized and tested new highly fluorescent metal organic framework (MOF) materials based on stilbene dicarboxylic acid as a linker. The crystal structure and porosity of the product are dependent on synthetic conditions and choice of solvent and a low-density cubic form has been identified by x-ray diffraction. In this work we report experiments demonstrating scintillation properties of these crystals. Bright proton-induced luminescence with large shifts relative to the fluorescence excitation spectra were recorded, peaking near 475 nm. Tolerance to fast proton radiation was evaluated by monitoring this radio-luminescence to absorbed doses of several hundred MRAD.
Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accurate data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are reached concerning the factors affecting the growth rate in on-line APCVD reactors. In addition, a substantial body of data was generated that can be used to model many different industrial tin oxide coating processes. These data include the most extensive compilation of thermochemistry for gas-phase tin-containing species as well as kinetic expressions describing tin oxide growth rates over a wide range of temperatures, pressures, and reactant concentrations.
This report summarizes the results of a five-year effort to understand the mechanisms and develop models that predict the corrosion of refractories in oxygen-fuel glass-melting furnaces. Thermodynamic data for the Si-O-(Na or K) and Al-O-(Na or K) systems are reported, allowing equilibrium calculations to be performed to evaluate corrosion of silica- and alumina-based refractories under typical furnace operating conditions. A detailed analysis of processes contributing to corrosion is also presented. Using this analysis, a model of the corrosion process was developed and used to predict corrosion rates in an actual industrial glass furnace. The rate-limiting process is most likely the transport of NaOH(gas) through the mass-transport boundary layer from the furnace atmosphere to the crown surface. Corrosion rates predicted on this basis are in better agreement with observation than those produced by any other mechanism, although the absolute values are highly sensitive to the crown temperature and the NaOH(gas) concentration at equilibrium and at the edge of the boundary layer. Finally, the project explored the development of excimer laser induced fragmentation (ELIF) fluorescence spectroscopy for the detection of gas-phase alkali hydroxides (e.g., NaOH) that are predicted to be the key species causing accelerated corrosion in these furnaces. The development of ELIF and the construction of field-portable instrumentation for glass furnace applications are reported and the method is shown to be effective in industrial settings.
The thermochemistry of the transition-metal fluorides and chlorides MF{sub n} and MCl{sub n} (M = Cr, Mn, Fe; n = 1, 2) has been characterized by high-level ab initio electronic structure methods. Geometries and harmonic vibrational frequencies were computed at the B3LYP level of theory using triple-{zeta} basis sets including diffuse and polarization functions. Heats of formation were computed from isogyric reaction energies at the CCSD(T) level using high-quality basis sets, including corrections for core-valence correlation and scalar relativistic effects. To investigate the possible linearity of the ground states of CrCl{sub 2} and CrF{sub 2}, we performed geometry optimizations for these species at the CCSD(T) level using large basis sets. In both cases, a bent ({sup 5}B{sub 2}) minimum structure was located, but the bent structure is only slightly below the linear form, which was found to be a transition state. For all of the investigated halides, polynomial fits were carried out for the heat capacity and the standard enthalpy and entropy in the 300-3000 K temperature range.