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Separation of Fischer-Tropsch Wax from Catalyst by Supercritical Extraction

Description: The proposed process of using supercritical fluid extraction in conjunction with the Fischer-Tropsch slurry bubble column reactor has been examined using the ASPEN Plus simulator by the research group at North Carolina State University. Qualitative results have been obtained for varying the following process parameters: solvent-to-wax ratio, solvent type (pentane or hexane), extraction temperature and pressure, and recovery unit temperature and pressure. The region of retrograde behavior was determined for pentane and hexane. Initial results show hexane to be the superior solvent; compared to pentane, hexane requires lower quantities of solvent makeup (the amount of solvent which needs to be added to account for solvent that cannot be recycled), and also results in a lower average molecular weight of slurry in the reactor. Studies indicate that increasing the extraction temperature, extraction pressure, recovery temperature, or solvent to wax ratio decreases the amount solvent makeup required. Decreasing the recovery pressure was found to decrease the makeup flowrate.
Date: January 31, 1997
Creator: Joyce, P.C. & Thies, M.C.
Partner: UNT Libraries Government Documents Department

Solvent Extraction of Chemical Attribution Signature Compounds from Painted Wall Board: Final Report

Description: This report summarizes work that developed a robust solvent extraction procedure for recovery of chemical attribution signature (CAS) compound dimethyl methyl phosphonate (DMMP) (as well as diethyl methyl phosphonate (DEMP), diethyl methyl phosphonothioate (DEMPT), and diisopropyl methyl phosphonate (DIMP)) from painted wall board (PWB), which was selected previously as the exposed media by the chemical attribution scientific working group (CASWG). An accelerated solvent extraction approach was examined to determine the most effective method of extraction from PWB. Three different solvent systems were examined, which varied in solvent strength and polarity (i.e., 1:1 dichloromethane : acetone,100% methanol, and 1% isopropanol in pentane) with a 1:1 methylene chloride : acetone mixture having the most robust and consistent extraction for four original target organophosphorus compounds. The optimum extraction solvent was determined based on the extraction efficiency of the target analytes from spiked painted wallboard as determined by gas chromatography x gas chromatography mass spectrometry (GCxGC-MS) analysis of the extract. An average extraction efficiency of approximately 60% was obtained for these four compounds. The extraction approach was further demonstrated by extracting and detecting the chemical impurities present in neat DMMP that was vapor-deposited onto painted wallboard tickets.
Date: October 29, 2009
Creator: Wahl, Jon H. & Colburn, Heather A.
Partner: UNT Libraries Government Documents Department

Pentan isomers compound flame front structure

Description: The fuels (hexane, pentane, diethyl ether) and conditions investigated in this study are relevant to engine knock in spark- ignition engines. A review is provided of the field of low temperature hydrocarbon oxidation. Studies were made of radical and stable intermediate distribution in the front of cool flames: Maximum concentrations of H atoms and peroxy radicals were observed in the luminous zone of the cool flame front. Peroxy radicals appear before the luminous zone at 430 K due to diffusion. H atoms were found in cool flames of butane and hexane. H atoms diffuses from the luminous zone to the side of the fresh mixture, and they penetrate into the fresh mixture to a small depth. Extension of action sphear of peroxy radicals in the fresh mixture is much greater than that of H atoms due to their small activity and high concentrations.
Date: August 13, 1995
Creator: Mansurov, Z. A.; Mironenko, A. W.; Bodikov, D. U. & Rachmetkaliev, K. N.
Partner: UNT Libraries Government Documents Department

Assessing and Managing the Risks of Fuel Compounds: Ethanol Case Study

Description: We have implemented a suite of chemical transport and fate models that provide diagnostic information about the behavior of ethanol (denoted EtOH) and other fuel-related chemicals released to the environment. Our principal focus is on the impacts to water resources, as this has been one of the key issues facing the introduction of new fuels and additives. We present analyses comparing the transport and fate of EtOH, methyl tertiary butyl ether (MTBE), and 2,2,4 trimethyl pentane (TMP) for the following cases (1) discharges to stratified lakes, subsurface release in a surficial soil, (3) cross-media transfer from air to ground water, and (4) fate in a regional landscape. These compounds have significantly different properties that directly influence their behavior in the environment. EtOH, for example, has a low Henry's law constant, which means that it preferentially partitions to the water phase instead of air. An advantageous characteristic of EtOH is its rapid biodegradation rate in water; unlike MTBE or TMP, which degrade slowly. As a consequence, EtOH does not pose a significant risk to water resources. Preliminary health-protective limits for EtOH in drinking water suggest that routine releases to the environment will not result in levels that threaten human health.
Date: February 4, 2002
Creator: Layton, D.W. & Rice, D.W.
Partner: UNT Libraries Government Documents Department

Fischer Tropsch synthesis in supercritical fluids. Quarterly technical progress report, April 1, 1995--June 30, 1995

Description: Our objective for this quarter was to study the effect of co-feeding a 1-olefin on the Ruhrchemie catalyst activity and selectivity, during-both conventional Fisher-Tropsch synthesis (FTS) and FTS under supercritical conditions. We used propane as the supercritical fluid and 1-dodecene (1-C{sub 12}H{sub 24}) in this test. Motivation for this study was the work of Fujimoto and co-workers who reported that suppression of methane and enhancement of high molecular weight hydrocarbons selectivities occurs with co-feeding of 1-olefins (1-heptene, 1-tetradecene, or 1-hexadecene) during FTS under supercritical conditions, but not during the conventional FTS (Co-La catalyst supported on silica in supercritical n-pentane).The diffusion coefficients of products in supercritical fluids is discussed.
Date: May 1, 1996
Creator: Akgerman, A. & Bukur, D.B.
Partner: UNT Libraries Government Documents Department

Molecular control of electron and hole transfer processes: Theory and applications

Description: Recent decades have seen remarkable advances in microscopic understanding of electron transfer (ET) processes in widely ranging contexts, including solid-state, liquid solution, and complex biological assemblies. The primary goal of this chapter is to report recent advances in the modeling, calculation, and analysis of electronic coupling in complex molecular aggregates, thereby allowing an assessment of current progress toward the goal of molecular-level control and design. The control of electron transfer kinetics (i.e., enhancing desired processes, while inhibiting others) involves, of course, system energetics (especially activation and reorganization energies) as well as electronic coupling, which is most directly relevant only after the system has reached the appropriate point (or region) along the reaction coordinate. Nevertheless, to focus the discussion in this chapter, the authors will consider such energetics, and the associated molecular and solvent coordinates which control then, only to the extent that they bear on the analysis of the electronic coupling. In the following sections they first discuss the formulation of basic ET models, including the definition of initial and final states, the role of orbitals and 1-particle models in a many-electron context, the utility of various effective Hamiltonians, and the role of vibronic as well as purely electronic effects. With these theoretical tools in hand, they then examine very recent applications to complex molecular systems using the techniques of computational quantum chemistry, followed by detailed analysis of the numerical results. They then conclude with some comments regarding the current ``state of the art`` and remaining challenges.
Date: February 1, 1996
Creator: Newton, M.D. & Cave, R.J.
Partner: UNT Libraries Government Documents Department

Extents of alkane combustion during rapid compression leading to single and two stage ignition

Description: Extents of reactant consumption have been measured during the course of spontaneous ignition following rapid compression of N-pentane and N-heptane and also of PRF 60 (N-heptane = i-octane, 2.2.4 trimethylpentane) in stoichiometric mixtures with air. Compressed gas temperatures of 720-750 K and 845-875 K were studied at reactant densities of 131 mol m{sup minus 3}. At the lower gas temperature there was no evidence of reactant consumption during the course of the compression stroke. Two-stage ignition occurred at these temperatures, but only modest proportions of n-pentane were consumed during the first stage (< 15%) whereas about 40% of proportions of n- heptane reacted under the same conditions. At the higher compressed gas temperature the oxidation of n-pentane began only after the piston had stopped, whereas more than 30% of the n-heptane had already been consumed in the final stage of the compression stroke. The behavior of the PRF 60 mixture differed somewhat from that of N- pentane despite the similarly of the research octane numbers. Although there was a preferential oxidation of n-heptane at T{sub c} = 850K, which persisted throughout the early development of spontaneous ignition during the post-compression period, oxidation of both components of the PRF 60 mixture began before the piston had stopped. Numerical simulations of the spontaneous ignition under conditions resembling those of the rapid compression experiments show that the predicted reactivity from detailed kinetics are consistent with the observed features. Insights into the kinetic interactions that give rise to the relative reactivities of the primary reference fuel components are established
Date: February 1, 1996
Creator: Cox, A.; Griffiths, J.F.; Mohamed, C.; Curran, H.; Pitz, W.J. & Westbrook, C.K.
Partner: UNT Libraries Government Documents Department

Vapor space characterization of waste Tank 241-BY-106 (in situ): Results from samples collected on 5/4/94 and 5/5/94

Description: This report describes inorganic and organic analyses results from in situ samples obtained from the headspace of the Hanford waste storage Tank 241-BY-106 (referred to as Tank BY-106). The results described here were obtained to support safety and toxicological evaluations. A summary of the results for inorganic and organic analytes is listed in Table 1. Detailed descriptions of the results appear in the text. Quantitative results were obtained for the inorganic compounds NH{sub 3}, NO{sub 2}, NO, HCN, and H{sub 2}O. Sampling for sulfur oxides was not requested. Organic compounds were also quantitatively determined. Twenty-three organic tentatively identified compounds (TICS) were observed above the detection limit of (ca.) 10 ppbv, but standards for most of these were not available at the time of analysis, and the reported concentrations are semiquantitative estimates. In addition, the authors looked for the 41 standard TO-14 analytes. Of these, only a few were observed above the 2-ppbv detection limit. The 10 organic analytes with the highest estimated concentrations are listed in Table 1. The 10 analytes account for approximately 64% of the total organic components in Tank BY-106. Tank BY-106 is on the Ferrocyanide Watch List.
Date: April 1, 1995
Creator: Clauss, T.W.; Ligotke, M.W.; Pool, K.H.; Lucke, R.B.; McVeety, B.D.; Sharma, A.K. et al.
Partner: UNT Libraries Government Documents Department

Chemical kinetic modelling of hydrocarbon ignition

Description: Chemical kinetic modeling of hydrocarbon ignition is discussed with reference to a range of experimental configurations, including shock tubes, detonations, pulse combustors, static reactors, stirred reactors and internal combustion engines. Important conditions of temperature, pressure or other factors are examined to determine the main chemical reaction sequences responsible for chain branching and ignition, and kinetic factors which can alter the rate of ignition are identified. Hydrocarbon ignition usually involves complex interactions between physical and chemical factors, and it therefore is a suitable and often productive subject for computer simulations. In most of the studies to be discussed below, the focus of the attention is placed on the chemical features of the system. The other physical parts of each application are generally included in the form of initial or boundary conditions to the chemical kinetic parts of the problem, as appropriate for each type of application being addressed.
Date: August 25, 1995
Creator: Westbrook, C.K.; Pitz, W.J.; Curran, H.J.; Gaffuri, P. & Marinov, N.M.
Partner: UNT Libraries Government Documents Department


Description: The molecular structure and microstructure of a suite of fine particulate matter (PM) samples produced by the combustion of residual fuel oil and diesel fuel were investigated by an array of analytical techniques. Some of the more important results are summarized below. Diesel PM (DPM): A small diesel engine test facility was used to generate a suite of diesel PM samples from different fuels under engine load and idle conditions. C XANES, {sup 13}C NMR, XRD, and TGA were in accord that the samples produced under engine load conditions contained more graphitic material than those produced under idle conditions, which contained a larger amount of unburned diesel fuel and lubricating oil. The difference was enhanced by the addition of 5% of oxygenated compounds to the reference fuel. Scanning transmission x-ray micro-spectroscopy (STXM) was able to distinguish particulate regions rich in C=C bonds from regions rich in C-H bonds with a resolution of {approx}50 nm. The former are representative of more graphitic regions and the latter of regions rich in unburned fuel and oil. The dominant microstructure observed by SEM and TEM consisted of complex chain-like structures of PM globules {approx}20-100 nm in mean diameter, with a high fractal dimension. High resolution TEM revealed that the graphitic part of the diesel soot consisted of onion-like structures made up of graphene layers. Typically 3-10 graphene layers make up the ''onion rings'', with the layer spacing decreasing as the number of layers increases. ROFA PM: Residual oil fly ash (ROFA) PM has been analyzed by a new approach that combines XAFS spectroscopy with selective leaching procedures. ROFA PM{sub 2.5} and PM{sub 2.5+} produced in combustion facilities at the U.S. EPA National Risk Management Research Laboratory (NRML) were analyzed by XAFS before and after leaching with water, acid (1N HCl), and pentane. Both water ...
Date: July 31, 2003
Creator: Huffman, Gerald P.; Huggins, Frank E.; Shah, Naresh; Braun, Artur; Chen, Yuanzhi; Robertson, J. David et al.
Partner: UNT Libraries Government Documents Department

Sensing liquid properties with shear-mode resonator sensors

Description: Liquid properties are measured from the changes they induce in the resonant frequency and damping of thicknessshear mode quartz resonators. A smooth-surfaced resonator viscously entrains the contacting fluid and responds to the density-viscosity product. Separation of density and viscosity is accomplished using two devices: one with a smooth surface and one with a corrugated surface that traps fluid. By observing the difference in stored and dissipated energies in the contacting fluid, its non-Newtonian characteristics can also be determined.
Date: June 1, 1995
Creator: Martin, S.J.; Cernosek, R.W. & Spates, J.J.
Partner: UNT Libraries Government Documents Department

Final Technical Report: Effects of Impurities on Fuel Cell Performance and Durability

Description: The main objectives of this project were to investigate the effect of a series of potential impurities on fuel cell operation and on the particular components of the fuel cell MEA, to propose (where possible) mechanism(s) by which these impurities affected fuel cell performance, and to suggest strategies for minimizing these impurity effects. The negative effect on Pt/C was to decrease hydrogen surface coverage and hydrogen activation at fuel cell conditions. The negative effect on Nafion components was to decrease proton conductivity, primarily by replacing/reacting with the protons on the Bronsted acid sites of the Nafion. Even though already well known as fuel cell poisons, the effects of CO and NH3 were studied in great detail early on in the project in order to develop methodology for evaluating poisoning effects in general, to help establish reproducibility of results among a number of laboratories in the U.S. investigating impurity effects, and to help establish lower limit standards for impurities during hydrogen production for fuel cell utilization. New methodologies developed included (1) a means to measure hydrogen surface concentration on the Pt catalyst (HDSAP) before and after exposure to impurities, (2) a way to predict conductivity of a Nafion membranes exposed to impurities using a characteristic acid catalyzed reaction (methanol esterification of acetic acid), and, more importantly, (3) application of the latter technique to predict conductivity on Nafion in the catalyst layer of the MEA. H2-D2 exchange was found to be suitable for predicting hydrogen activation of Pt catalysts. The Nafion (ca. 30 wt%) on the Pt/C catalyst resides primarily on the external surface of the C support where it blocks significant numbers of micropores, but only partially blocks the pore openings of the meso- and macro-pores wherein lie the small Pt particles (crystallites). For this reason, even with 30 wt% Nafion ...
Date: November 11, 2011
Creator: Goodwin, James G., Jr.; Colon-Mercado, Hector; Hongsirikarn, Kitiya & Zhang, Jack Z.
Partner: UNT Libraries Government Documents Department

Contribution of electronically excited states to the radiation chemistry of organic systems. Progress report, September 1, 1978-August 31, 1979

Description: The effect of n-perfluorohexane to quench both the emission and photoionization current of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) in isooctane and in tetramethylsilane has been shown to be consistent with an interaction of perfluorohexane with some relatively long-lived, coherently excited state of TMPD that is generated at the photoionization threshold and which decays either to the emitting state of TMPD or to a geminate ion-pair. The 0/sup 0/ and 90/sup 0/ electron impact spectra of the stable isomers of C/sub 3/, C/sub 4/, and C/sub 5/ saturated hydrocarbons are being determined. Preliminary results show large structural effects on the lowest Rydberg singlet-triplet splittings. Two photon excited emission spectra of decalin, bicyclohexyl, and cyclohexane have been observed in good agreement with previously reported one-photon spectra. A weak emission from propylene has also been detected. From measurement of the photosensitized singlet emission of p-xylene by bicyclohexyl excited at 1740 A, it appears that the bicyclohexyl triplet contributes importantly to the sensitization. Also previously reported deviations from Stern-Volmer behavior in the fast-electron-excited process are found too in the photo-excited process (at 1740 A) and therefore cannot be attributed exclusively to ionic processes. The much larger ratio of excimer to monomer intensity in polystyrene as compared to neat liquid benzene appears to be due mainly to a reduced entropy of dissociation of the excimer when the phenyls are tied to the polymer backbone. Excimers formed therefore from distant phenyl groups may manifest themselves at high quencher concentrations and thus provide a new technique for probing polymer conformation.
Date: January 1, 1979
Creator: Lipsky, S.
Partner: UNT Libraries Government Documents Department

Variable pressure supercritical Rankine cycle for integrated natural gas and power production from the geopressured geothermal resource

Description: A small-scale power plant cycle that utilizes both a variable pressure vaporizer (heater) and a floating pressure (and temperature) air-cooled condenser is described. Further, it defends this choice on the basis of classical thermodynamics and minimum capital cost by supporting these conclusions with actual comparative examples. The application suggested is for the geopressured geothermal resource. The arguments cited in this application apply to any process (petrochemical, nuclear, etc.) involving waste heat recovery.
Date: March 1, 1982
Creator: Goldsberry, F.L.
Partner: UNT Libraries Government Documents Department

Resonance-fluorescence kinetic study of oxygen atom + hydrocarbon reactions, V: O(/sup 3/P) + Neopentane (415-922K)

Description: Absolute values of the rate constants for the reaction of O(/sup 3/P) with neo-C/sub 5/H/sub 12/ were determined directly with the use of the complementary techniques: flash photolysis (FP) and discharge flow (DF). The O-atoms were monitored via resonance fluorescence (RF) in both systems, allowing experiments to be carried out at very low (0). Secondary reactions were averted in this way, and the rate data thus obtained were stoichiometry-free. The DF-RF experiments were performed over the temperature range, 427-922K. Over the common range of temperature the absolute rate constants were in excellent agreement. The combined set of data from 415-922K is well described by k/sub 1/ = (1.52 +- 0.28) x 10/sup -10/ exp (-7143 +- 196/RT) cm/sup 3/ molecule/sup -1/ s/sup -1/ where R is expressed in cal mole/sup -1/ K/sup -1/ and the errors are taken at the two standard deviation level (95% confidence). The bond energy-bond order (BEBO) method along with activated complex theory was applied to the title reaction, and satisfactory agreement with experimental rate constants was obtained.
Date: January 1, 1982
Creator: Michael, J.V.; Keil, D.G. & Klemm, R.B.
Partner: UNT Libraries Government Documents Department

Geothermal binary-cycle working-fluid properties information. Annual report

Description: The research discussed was performed prior to December 31, 1979. The report was not released until September 30, 1981, so that pressure-enthalpy diagrams for a number of potential geothermal binary cycle working fluids could be prepared in SI units. Efforts were directed principally to working fluid thermophysical property correlation and presentation of properties information. Pressure-enthalpy diagrams are presented for propane, normal butane, isobutane, normal pentane, isopentane and propylene. Generalized correlations are presented for the thermodynamic and transport properties of hydrocarbon pure and mixture working fluids. Specific correlations are presented for the thermodynamic properties of 27 fluids and for the viscosity and thermal conductivity of hydrocarbons including isobutane and isopentane.
Date: September 30, 1981
Creator: Starling, K.E.; Kumar, K.H.; Malik, Z.I.; Batson, B. & Plumb, P.
Partner: UNT Libraries Government Documents Department

Synthesis, chemistry, and catalytic activity of complexes of lanthanide and actinide metals in unusual oxidation states and coordination environments. Progress report, February 1, 1977--January 31, 1978

Description: Research devoted to synthesis of new classes of lanthanide and actinide complexes is reported. Co-condensation of lanthanide metals with 1,3-butadiene (1,3-C/sub 4/H/sub 6/) or 2,3-dimethyl-1,3-butadiene (2,3-(CH/sub 3/)/sub 2/-1,3-C/sub 4/H/sub 4/) produces three types of organolanthanide complexes differentiated by their solubility in pentane, toluene and tetrahydrofuran (THF). The THF soluble species are formed in highest yield and have been most completely characterized. Elemental analysis shows that when butadiene is the ligand, complexes of empirical formula Ln(C/sub 4/H/sub 6/)/sub 3/ (Ln = Nd, Sm, Er) are obtained. When dimethylbutadiene is used, Ln((CH/sub 3/)/sub 2/C/sub 4/H/sub 4/)/sub 2/ is obtained (Ln = La, Nd, Sm, Er). These compounds differ from all other organolanthanide complexes in several respects. First, it is unusual to be able to obtain such good analytical data. Generally, for organolanthanides, incomplete carbon and hydrogen combustion is observed. Second, the stoichiometries are difficult to reconcile with known lanthanide chemistry. If the dienes coordinate as ..pi..-ligands, the metals are formally zero-valent. If the dienes coordinate as dialkyl-2-butene moieties, the metals must be in the +6 oxidation state in the butadiene series and the +4 oxidation state in the dimethylbutadiene series. The physical properties of these new complexes are also unusual. The sharp, line-like, 4f-4f optical transitions normally observed for lanthanide complexes are not observed in the visible and near infrared regions. Instead a single broad band dominates the spectrum. The room temperature magnetic moments are similarly not consistent with known Ln/sup 3 +/ species. Most unusual in this respect is the lanthanum complex, which is the first paramagnetic organolanthanum complex ever observed. Further investigations of diene reactions with lanthanides in chemical reduction syntheses are summarized. (JRD)
Date: October 1, 1977
Creator: Evans, W.J.
Partner: UNT Libraries Government Documents Department

Thumb tack physical model evaluation of polystyrene bead foam as an encapsulant for electronic packages

Description: A physical model in the shape of a thumb tack is used to measure forces on electronic component lead wires when soldered into printed wiring boards. Encapsulation of electronic packages in polystyrene bead foam of 0.2, 0.3, 0.4, 0.5, and 0.6 g/cm/sup 3/ densities was evaluated. No solder joint damage was seen. Crushing pressures on metal transistors also were safe for all densities. Experimental data agreed well with theoretical calculations based on the concept of constrained thermal expansion.
Date: March 1, 1980
Creator: Fossey, D.J. & Swanson, G.D.
Partner: UNT Libraries Government Documents Department