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Low severity coal liquefaction promoted by cyclic olefins

Description: Low severity coal liquefaction allows for solubilization of coal with reduced gas make. These lower severity conditions may result in some selective bond rupture. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin, which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene. These compounds are hydroaromatics without aromatic rings and have been shown to be highly effective donors. The objective of the work performed in this study during this quarter was to evaluate reaction parameters for low severity liquefaction reactions using the cyclic olefin, hexahydroanthracene, and the aromatic, anthracene. These model compounds were reacted under a variety of conditions to evaluate their reactivity without coal. The reactions were performed under both thermal and catalytic conditions. Finely divided catalysts from different molybdenum precursors were used to determine their activity in promoting hydrogenation and hydrogen transfer at low severity conditions. The catalysts used were Molyvan L, sulfurized oxymolybdenum dithiocarbamate, molybdenum naphthenate, and Molyvan 822, organo molybdenum dithiocarbamate.
Date: July 27, 1992
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Studies of transition states and radicals by negative ion photodetachment

Description: Negative ion photodetachment is a versatile tool for the production and study of transient neutral species such as reaction intermediates and free radicals. Photodetachment of the stable XHY{sup {minus}} anion provides a direct spectroscopic probe of the transition state region of the potential energy surface for the neutral hydrogen transfer reaction X + HY {yields} XH + Y, where X and Y are halogen atoms. The technique is especially sensitive to resonances, which occur at a specific energy, but the spectra also show features due to direct scattering. We have used collinear adiabatic simulations of the photoelectron spectra to evaluate trail potential energy surfaces for the biomolecular reactions and have extended the adiabatic approach to three dimensions and used it to evaluate empirical potential energy surfaces for the I + Hl and Br + HI reactions. In addition, we have derived an empirical, collinear potential energy surface for the Br + HBr reaction that reproduces our experimental results and have extended this surface to three dimensions. Photodetachment of a negative ion can be also used to study neutral free radicals. We have studied the vibrational and electronic spectroscopy of CH{sub 2}NO{sub 2} by photoelectron spectroscopy of CH{sub 2}NO{sub 2}{sup {minus}}, determining the electron affinity of CH{sub 2}NO{sub 2}, gaining insight on the bonding of the {sup 2}B{sub 1} ground state and observing the {sup 2}A{sub 2} excited state for the first time. Negative ion photodetachment also provides a novel and versatile source of mass-selected, jet-cooled free radicals. We have studied the photodissociation of CH{sub 2}NO{sub 2} at 270, 235, and 208 nm, obtaining information on the dissociation products by measuring the kinetic energy release in the photodissociation.
Date: December 1, 1991
Creator: Metz, R. B.
Partner: UNT Libraries Government Documents Department

Solvent tailoring in coal liquefaction. Quarterly report, October 1983-December 1983

Description: The contribution of transferable hydrogen in coal-derived solvents to coal conversion was investigated in a two-step process. Initially, the amount of transferable hydrogen in the coal-derived solvents was analyzed by spectroscopic methods and by catalytic dehydrogenation. The spectroscopic methods included carbon magnetic resonance, proton magnetic resonance as well as a combination of these two methods. Three of the methods gave nearly equivalent quantities for the amount of transferable hydrogen present in the complex coal liquids. Coal conversion determined in each of the coal-derived solvents was correlated to the amount of transferable hydrogen present. The contribution of transferable hydrogen is a significant factor in coal dissolution and the presence of saturates and hexane insolubles compounds in these solvents may have a detrimental effect on coal dissolution. 20 references, 9 figures, 2 tables.
Date: July 1, 1983
Creator: Tarrer, A. R.; Curtis, C. W.; Guin, J. A. & Williams, D. C.
Partner: UNT Libraries Government Documents Department

Solvent tailoring in coal liquefaction. Quarterly report, July-September 1983

Description: A series of twenty-three aromatic compounds were ranked for their donor solvent efficacy for the dissolution of Western Kentucky No. 9/14 coal. The transfer of hydrogen from the solvent to the coal fragments, as measured by coal conversion, was examined at three levels of available hydrogen. The hydrogen donors are ranked according to their ability to convert coal to THF solubles. Aromatic analogs of the donors showed little ability to convert coal to THF solubles. Factors which influence hydrogen donation include the presence of heteroatoms or substituents both internal and external to the aromatic or hydroaromatic rings, the degree of hydrogenation, the aromaticity or nonaromaticity of the hydroaromatics, and the presence of five-membered rings. A relationship between heats of formation and hydrogen donor ability is shown for hydroaromatics within two ring or three ring homologous series. A model hydrogen acceptor, benzophenone, is also used to rank donors. No correlation exists in the ranking of hydrogen donors by the model acceptor used in this work and in other experimental studies and that obtained by conversion of Western Kentucky coal at typical liquefaction conditions. 24 references.
Date: January 1, 1983
Creator: Tarrer, A. R.; Curtis, C. W.; Guin, J. A. & Williams, D. C.
Partner: UNT Libraries Government Documents Department

Simulations of Fluid Nitromethane Under Extreme Conditions

Description: We report density functional molecular dynamics simulations to determine the early chemical events of hot (T = 3000 K) and dense (1.97 g/cm{sup 3}, V/V{sub 0} = 0.68) nitromethane (CH{sub 3}NO{sub 2}). The first step in the decomposition process is an intermolecular proton abstraction mechanism that leads to the formation of CH{sub 3}NO{sub 2}H and the aci ion H{sub 2}CNO{sub 2}{sup -}, in support of evidence from static high-pressure and shock experiments. An intramolecular hydrogen transfer that transforms nitromethane into the aci acid form, CH{sub 2}NO{sub 2}H, accompanies this event. This is the first confirmation of chemical reactivity with bond selectivity for an energetic material near the condition of fully reacted specimen. We also report the decomposition mechanism followed up to the formation of H{sub 2}O as the first stable product.
Date: July 15, 2003
Creator: Fried, L E; Reed, E J & Manaa, M R
Partner: UNT Libraries Government Documents Department

Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, April--June 1993

Description: Low-severity coal liquefaction allows for the solubilization of coal with reduced gas make. The idea being tested in this research is whether selective bond rupture occurs during liquefaction at low temperatures that can be satisfied by hydrogen donation from highly active hydrogen donor compounds. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective hydrogen donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin (ISO), which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene (HHA). These compounds have been shown to highly effective donors (Bedell and Curtis, 1991) which release their hydrogen at fairly low temperatures, in the 200 to 300{degree}C range. ISO has been shown to be much more effective than its hydroaromatic analogue tetralin (TET) in releasing hydrogen at low temperatures and transferring that hydrogen to an acceptor molecule or to coal (Bedell and Curtis, 1991). Likewise, at 380{degree}C, the ability of HHA to release hydrogen in both N{sub 2} and H{sub 2} atmospheres was greater than a comparative hydroaromatic compound, dihydroanthracene (DHA). However, when an acceptor molecule or coal was present, DHA was as or more active than HHA in transferring hydrogen (Bedell et al., 1993). In another study, at equivalent reaction conditions and in the presence of anthracene (ANT) as a hydrogen acceptor, ISO released more than 200 times as much hydrogen as TET and HHM released 18 to 25 times as much hydrogen as DHA (Wang, 1992).
Date: November 1, 1993
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, January--March 1992

Description: The naphthalene hydrogenation performed thermally at 350 and 400{degrees}C showed no reactivity of the naphthalene. The Molyvan L catalyst precursor promoted a small amount of hydrogenation of naphthalene at 400{degrees}C as shown in Table 1. Reaction at the higher initial pressure of 1250 psi resulted in slightly more conversion of naplithalene and a higher production of tetralin but no decalin was observed. The naphthalene hydrogenation reactions with Molyvan L without sulfur yielded a slightly higher % HYD of naphthalene than did the reactions with sulfur. Likewise, the reactions with an initial hydrogen pressure of 1250 psi yielded a higher % HYD of naphthalene than did the reaction with 1000 psi, regardless of whether sulfur was present. The Molyvan 822 catalyst precursor was substantially more active at 400{degrees}C than at 350{degrees}C as presented in Table 2. The presence of sulfur also promoted the activity of Molyvan 822 as a catalyst. Tetralin was the product and was produced in substantial quantities at 400{degrees}C. Molyvan 822 was much more active for naphthalene hydrogenation than was Molyvan L under equivalent conditions. For example, at 400{degrees}C with sulfur the reactions with Molyvan 822 produced 33.5% HYD while Molyvan L yielded 1.8% HYD. With Molyvan L, the less active catalyst, the effect tile mode of agitation (vertical or horizontal) was minimal.
Date: October 1, 1992
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

High conversion of coal to transportation fuels for the future with low HC gas production. Progress report No. 3, April 1--June 30, 1993

Description: The objective of the current research in coal liquefaction is to produce a synthetic crude from coal at a cost lower than $30.00 per barrel (Task A). A second objective is to produce a fuel which is low in aromatics, yet of sufficiently high octane number for use in the gasoline-burning transportation vehicles of today. To meet this second objective, research was proposed for conversion of the highly-aromatic liquid product from coal conversion to a product high in isoparaffins, which compounds in the gasoline range exhibit a high octane number (Task B). Experimental coal liquefaction studies conducted in a batch microreactor in the laboratory have demonstrated potential for high conversions of coal to liquids with low yields of hydrocarbon (HC) gases, hence small consumption of hydrogen in the primary liquefaction step. Ratios of liquids/HC gases as high as 30/1, at liquid yields as high as 82% of the coal by weight, have been achieved. The principal objective of this work is to examine how nearly the authors may approach these results in a continuous-flow system, at a size sufficient to evaluate the process concept for production of transportation fuels from coal. Work to date is described.
Date: July 1, 1993
Creator: Wiser, W. H. & Oblad, A. G.
Partner: UNT Libraries Government Documents Department

Development of biological coal gasification (MicGAS Process)

Description: The overall goal of the project is to develop an advanced, clean coal biogasification (MicGAS) Process. The objectives of the research during FY 1993--94 were to: (1) enhance kinetics of methane production (biogasification, biomethanation) from Texas lignite (TxL) by the Mic-1 consortium isolated and developed at ARCTECH, (2) increase coal solids loading, (3) optimize medium composition, and (4) reduce retention time. A closer analysis of the results described here indicate that biomethanation of TxL at >5% solids loading is feasible through appropriate development of nutrient medium and further adaptation of the microorganisms involved in this process. Further understanding of the inhibitory factors and some biochemical manipulations to overcome those inhibitions will hasten the process considerably. Results are discussed on the following: products of biomethanation and enhance of methane production including: bacterial adaptation; effect of nutrient amendment substitutes; effects of solids loading; effect of initial pH of the culture medium; effect of hydrogen donors and carbon balance.
Date: October 1, 1994
Creator: Walia, D. S. & Srivastava, K. C.
Partner: UNT Libraries Government Documents Department

The role of the resid solvent in co-processing with finely divided catalysts. Quarterly report April--June 1993

Description: The primary purpose of the work performed this quarter was to establish under thermal and catalytic reaction conditions whether hydrogen transfer occurred between cycloalkane type structures that are present in resids and heteroatomic species that are present in coal and liquefied coal. The research this quarter focused upon evaluating benzophenone (BENZ) as a model acceptor for hydrogen that might be transferred from a cycloalkane, perhydropyrene (PHP), under coprocessing conditions. Hence, a number of reactions was performed in which BENZ was reacted alone in hydrogen and nitrogen atmospheres in the presence and absence of a catalytic agent, molybdenum naphthenate. Reactions were also performed using a combination of PHP and BENZ at a 1 to 1 weight ratio. Also performing this quarter were initial separations with petroleum resids. Two different resids were used, Maya and LHC-362. The literature was also surveyed to determine important characteristics that should be evaluated for selecting resids. The resids that are desired for this project are resids with high-, medium-, and low-naphthenic content. Different levels of asphaltenes are also desirable. Resids with these characteristics are currently being sought. The model compound PHP that had been commercially available as naphthene representative of resids is now no longer available. Hence, several scoping experiments were performed in order to determine conditions for synthesizing PHP. The synthesis procedure reported in US Patent 3,303,227 was used as a basis for this work. Although more than 85% PHP was synthesized, partially hydrogenated pyrenes were also produced which will require separation in order to obtain pure PHP.
Date: November 1, 1993
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Intrinsic barriers for H-atom transfer reactions involving hydrocarbons

Description: Intrinsic barriers (formally the barrier in the absence of driving force) for H-atom transfer reactions are key parameters in Evans-Polyanyi and Marcus equations for estimating exothermic reaction barriers and are fundamentally significant for the insight they provide about bond reorganization energies for formation of transition state structures. Although knowable from experiment, relatively few of these barriers have been measured due to experimental difficulties in measuring rates for identity reactions. Thus, the authors have used semiempirical Molecular Orbital theoretical methods (MNDO/PM3) to calculate barriers for a series of H-atom transfer identity reactions involving alkyl, alkenyl, arylalkyl and hydroaryl radicals and donors. Briefly stated, they find that barriers decrease with the degree of alkyl substitution at the radical site whereas barriers increase with the degree of conjugation with the radical site. Details of the methodology and analyses of how these barrier heights correlate with reactant and transition state properties will be presented and discussed.
Date: August 1, 1994
Creator: Camaioni, D. M.; Autrey, S. T. & Franz, J. A.
Partner: UNT Libraries Government Documents Department

Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, April--June 1992

Description: Low severity coal liquefaction allows for solubilization of coal with reduced gas make. These lower severity conditions may result in some selective bond rupture. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin, which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene. These compounds are hydroaromatics without aromatic rings and have been shown to be highly effective donors. The objective of the work performed in this study during this quarter was to evaluate reaction parameters for low severity liquefaction reactions using the cyclic olefin, hexahydroanthracene, and the aromatic, anthracene. These model compounds were reacted under a variety of conditions to evaluate their reactivity without coal. The reactions were performed under both thermal and catalytic conditions. Finely divided catalysts from different molybdenum precursors were used to determine their activity in promoting hydrogenation and hydrogen transfer at low severity conditions. The catalysts used were Molyvan L, sulfurized oxymolybdenum dithiocarbamate, molybdenum naphthenate, and Molyvan 822, organo molybdenum dithiocarbamate.
Date: July 27, 1992
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

High conversion of coal to transportationn fuels for the future with low HC gas production. Progress report No. 7, April 1--June 30, 1994

Description: The objective is to produce a Synthetic crude from coal at a cost lower than $30.00 per barrel (Task A). A second objective is to produce a fuel which is low in aromatics, yet of sufficiently high octane number for use in the gasoline-burning transportation vehicles of today. To meet this second objective, research was proposed, and funding awarded, for conversion of the highly-aromatic liquid product from coal conversion to a product high in isoparaffins, which compounds in the gasoline range exhibit a high octane number (Task B). Experimental coal liquefaction studies conducted in a batch microreactor in our laboratory have demonstrated potential for high conversions of coal to liquids with low yields of hydrocarbon (HC) gases, hence small consumption of hydrogen in the primary liquefaction step. Ratios of liquids/HC gases as high as 30/1, at liquid yields as high as 82% of the coal by weight, have been achieved. The principal objective of this work is to examine how nearly we may approach these results in a continuous-flow reactor system, at a size sufficient to evaluate the process concept for production of transportation fuels from coal. Accomplishments for this period are described.
Date: July 1, 1994
Creator: Wiser, W. H. & Oblad, A. G.
Partner: UNT Libraries Government Documents Department

Low severity coal liquefaction promoted by cyclic olefins. Quarterly report, January--March 1993

Description: The combination of some of these methods could further improve low severity conversion. It seems logical that a combination of a proven pretreatment technique with a good dissolution catalyst or a good hydrogen donor would increase reactivity. The importance of surface chemistry with yield and nature of reactions shown in early research indicates the physical importance of pretreatment. Swelling of the coal with an organic solvent improves the contact. This good contact is also important to slowing retrogressive reactions. The best conversions come when the initial products of liquefaction are preserved. In addition to the physical importance of pretreatment, there is a chemical advantage. Shams saw not only the effect of minimization of organic oxygen coupling reactions, but with his process there also seemed to be a demineralization. The minerals removed the catalysts for retrogressive reactions. The chemistry of liquefaction is still not well understood. Stansberry`s attempt to determine whether catalysts liberate species or just further decomposition was largely inconclusive. There was improvement in conversion so the catalysts seemingly assisted in bond breakage. These good catalytic effects were also seen in the work involving coprocessing. The most compelling factor in each of these procedures, is the ability of the coal to receive the hydrogen that it needs to be liquefied. Bedell and Curtis (1991) found that cyclic olefins gave their hydrogen up much more readily than did hydroaromatics. The coal conversion was a significantly improved. The combination of retrogressive reaction suppression and good hydrogen donability should provide for good coal conversion. It was this reasoning that influenced the decision to investigate a combination of the HCl/methanol pretreatment and the usage of cyclic olefins as hydrogen donors. The increased reactivity of the pretreated coal should enhance the effect of the hydrogen donability of the cyclic olefins.
Date: July 1, 1993
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

The role of the resid solvent in co-processing with finely divided catalysts. Quarterly report, January--March 1993

Description: The overall objective of this project is to evaluate the role of the resid in coprocessing. The primary purpose of this initial work was to establish under thermal and catalytic reaction conditions whether hydrogen transfer occurred between cycloalkane type structures that are present in resids and aromatics that are present in coal and liquefied coal. The research this quarter focused upon evaluating different reaction systems for performing model donor and model acceptor studies. The first system that was evaluated involved anthracene (ANT) as the model acceptor. Previous results had shown that ANT did not convert substantially in a thermal reaction at 380{degrees}C (Wang 1992); however, more was converted (about 50%) at 440{degrees}C. The results from the reactions performed last quarter indicated that substantial hydrogenation of ANT occurred thermally at 440{degrees}C; more than had been observed previously. The reactors that were used, though, had contained substantial amounts of catalysts prior to the performance of the thermal reactions. Hence, the passivity of the reactors was questioned and new reactors were fabricated. Some of the reactions using ANT were performed again and are reported herein. The second part of the work performed this quarter was to evaluate hydrogen transfer from the cycloalkane, perhydropyrene (PHP), to the aromatic phenanthrene (PHEN). Reactions were performed at a 1:1 PHP to PHEN weight ratio and with a 5:1 PHP to PHEN ratio. The reactions were performed thermally and catalytically at 400 and 425{degrees}C using molybdenum naphthenate and nickel octoate as catalysts. Reactions were also performed with added sulfur either as elemental sulfur or benzothiophene.
Date: August 1, 1993
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Studies of transition states and radicals by negative ion photodetachment

Description: Negative ion photodetachment is a versatile tool for the production and study of transient neutral species such as reaction intermediates and free radicals. Photodetachment of the stable XHY{sup {minus}} anion provides a direct spectroscopic probe of the transition state region of the potential energy surface for the neutral hydrogen transfer reaction X + HY {yields} XH + Y, where X and Y are halogen atoms. The technique is especially sensitive to resonances, which occur at a specific energy, but the spectra also show features due to direct scattering. We have used collinear adiabatic simulations of the photoelectron spectra to evaluate trail potential energy surfaces for the biomolecular reactions and have extended the adiabatic approach to three dimensions and used it to evaluate empirical potential energy surfaces for the I + Hl and Br + HI reactions. In addition, we have derived an empirical, collinear potential energy surface for the Br + HBr reaction that reproduces our experimental results and have extended this surface to three dimensions. Photodetachment of a negative ion can be also used to study neutral free radicals. We have studied the vibrational and electronic spectroscopy of CH{sub 2}NO{sub 2} by photoelectron spectroscopy of CH{sub 2}NO{sub 2}{sup {minus}}, determining the electron affinity of CH{sub 2}NO{sub 2}, gaining insight on the bonding of the {sup 2}B{sub 1} ground state and observing the {sup 2}A{sub 2} excited state for the first time. Negative ion photodetachment also provides a novel and versatile source of mass-selected, jet-cooled free radicals. We have studied the photodissociation of CH{sub 2}NO{sub 2} at 270, 235, and 208 nm, obtaining information on the dissociation products by measuring the kinetic energy release in the photodissociation.
Date: December 1, 1991
Creator: Metz, R. B.
Partner: UNT Libraries Government Documents Department

Restricted mass transport effects on free radical reactions

Description: Coal possesses a complex chemical and physical structure. The cross-linked, network structure can lead to alterations in normal thermally-induced, free-radical decay pathways as a consequence of restrictions on mass transport. Moreover, in coal liquefaction, access of an external hydrogen donor to a reactive radical site can be hindered by the substantial domains of microporosity present in coals. However, previous work indicates that diffusion effects do not appear to be playing an important role in this coal conversion chemistry. Several possible explanations for this phenomenon were advanced including the potential involvement of a hydrogen hopping/radical relay mechanism recently discovered model systems in the authors laboratories. The authors have employed silica-anchored compounds to explore the effects of restricted mass transport on the pyrolysis mechanisms of coal model compounds. In studies of two-component systems, cases have been discovered where radical centers can be rapidly relocated in the diffusionally constrained environment as a consequence of rapid serial hydrogen atom transfers. This chemistry can have substantial effects on thermal decomposition rates and on product selectivities. In this study, the authors examine additional surfaces to systematically investigate the impact of molecular structure on the hydrogen atom transfer promoted radical relay mechanism. Silica-attached 1,3-diphenylpropane ({approx}Ph(CH{sub 2}){sub 3}Ph, or {approx}DPP) was chosen as the thermally reactive component, since it can be considered prototypical of linkages in coal that do not contain weak bonds easily cleaved at coal liquefaction temperatures (ca. 4000 {degrees}C), but which crack at reasonable rates if benzylic radicals can be generated by hydrogen abstraction. The rate of such hydrogen transfers under restricted diffusion will be highly dependent on the structure and proximity of neighboring molecules.
Date: September 1, 1994
Creator: Buchanan, A. C. III; Britt, P. F. & Thomas, K. B.
Partner: UNT Libraries Government Documents Department

Investigation of the use of a recycle stream to mediate hydrogen transfer to improve the conversion of eastern oil shale to liquid products

Description: The processing of eastern oil shale has long been known to require the addition of hydrogen to increase the oil yield. Several researchers, have investigated the use of both high pressure hydrogen and hydrogen donor solvents. Much of the donor solvent work has used pure,compounds such as tetralin and has not addressed the use of-a more realistic solvent such as one derived from the production process itself. The work reported herein is for the research Task 1.2.2, Process Studies, in the Annual Project Plan, October l, 1990--September 30, 1991, of the Cooperative Agreement. In the study, a shale oil-derived, recycle oil was used to mediate the transfer of hydrogen to eastern oil shale. The work was divided into two main parts which correspond to the two main portions of the Hydrogen-Extraction (H-E{trademark}) process: (1) the shale oil extraction which involves the use of a donor solvent to aid in the extraction of the shale oil and (2) the regeneration of the donor solvent to a hydrogen-rich state ready for recycle. The results of the investigation to evaluate shale oil extraction using a shale oil-derived donor solvent suggest that temperature had the, greatest effort on organic conversion. At a temperature of 425{degrees}C (197{degrees}F), a yield of 130% of Fischer assay was obtained using tetralin as a donor solvent. At the same temperature, only 110% of Fischer assay could be obtained using a middle distillate as a donor solvent.
Date: June 1, 1944
Creator: Barbour, F. A.; Guffey, F. D.; Thomas, K. P. & Blake, R. F.
Partner: UNT Libraries Government Documents Department

Magnetic resonance studies of photo-induced electron transfer reactions. Final report, June 1, 1990--May 31, 1993

Description: Fourier Transform Electron Paramagnetic Resonance (FT EPR) is useful in study of photochemical reactions: a microwave pulse rotates the electron spin magnetization vector from z (magnetic field) into xy plane ({pi}/2 pulse); the time evolution of magnetization in xy plane, the free induction decay (FID), is sampled. Fourier transform of FID gives the frequency domain EPR spectrum of the free radicals, and the method is ideal for time-resolved studies of free radicals produced by pulsed-laser excitation. Investigations of electron transfer reactions focused on porphyrin (donor) - quinone (acceptor) systems. First, two hydrogen abstraction reactions were studied with FT EPR: photoreduction of acetone with 2-propanol, yielding the acetone ketyl radical, and the reaction of 2-propanol with t-butoxy radicals. Then, the FT EPR study of benzoquinone or duroquinone anion radicals generated by pulsed-laser induced electron transfer from zinc tetraphenylporphyrin (ZnTPP) or tetrasulfonated Zn(TPP), was carried out in homogeneous solution, micellar solutions, and silica gel. Finally, FT EPR was used to study electron transfer quenching of triplet C{sub 60} by electron donors.
Date: November 1, 1992
Creator: van Willigen, H.
Partner: UNT Libraries Government Documents Department

Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Quarterly report, September 26, 1989--December 26, 1989

Description: To gain a fundamental understanding of the role and importance of hydrogen transfer reactions in thermal and catalytic coprocessing by examining possible hydrogen donation from cycloalkane/aromatic systems and by understanding the chemistry and enhanced reactivity of hydrotreated residuum, as well as by enriching petroleum solvent with potent new donors, nonaromatic hydroaromatics, thereby promoting hydrogen transfer reactions in coprocessing. The detailed results of experiments performed on several subtasks during the quarter are presented.
Date: December 31, 1989
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Improved performance in coprocessing through fundamental and mechanistic studies in hydrogen transfer and catalysis. Final report, September 26, 1989--March 31, 1993

Description: The key results obtained from this research project are given: (1) Hydrogen transfer from naphthenes to aromatics, coal and resid occurred at coprocessing temperatures and in a N{sub 2} atmosphere; (2) Hydrogen donors ranked in reactivity as cyclic olefins (nonaromatic hydroaromatic compounds) > hydroaromatic compounds > naphthenes. This ranking held regardless of the type of atmosphere, hydrogen or nitrogen, used; (3) Resids reduced by the Birch method transferred substantially more hydrogen to the aromatic acceptor than did the parent resids under coprocessing conditions; (4) Hydropretreatment of resids resulted in enhanced coal conversion compared to the parent resid; (5) Addition of hydrogen donors such as cyclic olefins or hydroaromatic donors increased the amount of coal conversion during coprocessing. Cyclic olefins and the active hydroaromatic donor, dihydroanthracene, showed the highest level of hydrogen donability. Tetralin and octahydroanthracene showed low reactivity; (6) Reduced resids were more effective in coprocessing than the parent resids, in terms of enhanced coal conversion; (7) Thermal and catalytic reactivity of cyclic olefins under nitrogen and hydrogen atmospheres was much higher than conventional hydroaromatic donors when no aromatic acceptor was present; (8) Reactivity of hydrogen donors was dependent upon the reactivity of the acceptor as well as that of the donors; (9) Three-ring hydrogen donors, dihydroanthracene and hexahydroanthracene, were most effective for transferring hydrogen to the Argonne coals while octahydroanthracene was the least reactive; (10) The kinetics data obtained for thermal and catalytic reactions involving cyclic olefins and hydroaromatic donors were adequately modeled by pseudo-first order kinetics; and (11) {Delta}G values calculated for cyclic olefins and hydroaromatic donors based on kinetics data adequately represented the reactivity observed experimentally.
Date: December 31, 1993
Creator: Curtis, C. W.
Partner: UNT Libraries Government Documents Department

Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Progress report, November 1, 1991--October 31, 1992

Description: We are making progress on our investigation of the mechanism of olefin exchange with Os{sub 2}(C{sub 2}H{sub 4})(CO){sub 8}. We are probing this system by kinetic study of the reaction of Os{sub 2}(C{sub 2}H{sub 4})(CO){sub 8} with butyl acrylate (BA) under various pressures of ethylene.
Date: May 1, 1992
Creator: Norton, J. R.
Partner: UNT Libraries Government Documents Department