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MODELING OF SYNGAS REACTIONS AND HYDROGEN GENERATION OVER SULFIDES

Description: The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. During this study, adsorption reactions of H atoms and H{sub 2} molecules with MoS{sub 2}, both in molecular and solid form, have been modeled using high-level density functional theory. The relative stabilities of pure MoS{sub 2} edges were calculated and small clusters exhibiting properties of the edges were modeled. The results were finalized and published in the journal ''Surface Science''. Hydrogen adsorption energies on both the edges and the clusters were calculated, and the thermodynamics of hydrogen adsorption on both systems were evaluated. The adsorption locations and vibrational frequencies were also determined. These additional results were published in a second paper in ''Surface Science''. Most recently, the bonding and effect of alkali and transition metal ions was investigated on the MoS{sub 2} clusters. Potassium atoms bind to the clusters and increase the binding of hydrogen to the clusters while reducing the activation barriers for hydrogen adsorption. Silver attaches to the Mo7S14 cluster and donates its odd electron to the nearby Mo atoms and should have a similar effect to hydrogen as potassium does.
Date: October 1, 2004
Creator: Klier, Kamil; Spirko, Jeffery A. & Neiman, Michael L.
Partner: UNT Libraries Government Documents Department

Modeling of Syngas Reactions and Hydrogen Generation Over Sulfides

Description: The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. In this second year of study, high-level density functional theory was used to model the edge defect of MoS{sub 2} both with and without H atoms and H{sub 2} molecules absorbed on those edges. The structures and stabilities of the pure MoS{sub 2} edges were finalized and published. Several MoS{sub 2} cluster models were examined to provide insight into the behavior of the more complex edges. With that knowledge, the adsorption locations, energies, and vibrational frequencies of H adsorption were determined.
Date: September 17, 2003
Creator: Klier, Kamil; Spirko, Jeffery A. & Neiman, Michael L.
Partner: UNT Libraries Government Documents Department

Modeling of Syngas Reactions and Hydrogen Generation Over Sulfides

Description: The objective of the research is to analyze pathways of reactions of hydrogen with oxides of carbon over sulfides, and to predict which characteristics of the sulfide catalyst (nature of metal, defect structure) give rise to the lowest barriers toward oxygenated hydrocarbon product. Reversal of these pathways entails the generation of hydrogen, which is also proposed for study. In this first year of study, adsorption reactions of H atoms and H{sub 2} molecules with MoS{sub 2}, both in molecular and solid form, have been modeled using high-level density functional theory. The geometries and strengths of the adsorption sites are described and the methods used in the study are described. An exposed MO{sup IV} species modeled as a bent MoS{sub 2} molecule is capable of homopolar dissociative chemisorption of H{sub 2} into a dihydride S{sub 2}MoH{sub 2}. Among the periodic edge structures of hexagonal MoS{sub 2}, the (1{bar 2}11) edge is most stable but still capable of dissociating H{sub 2}, while the basal plane (0001) is not. A challenging task of theoretically accounting for weak bonding of MoS{sub 2} sheets across the Van der Waals gap has been addressed, resulting in a weak attraction of 0.028 eV/MoS{sub 2} unit, compared to the experimental value of 0.013 eV/MoS{sub 2} unit.
Date: September 17, 2002
Creator: Klier, Kamil; Spirko, Jeffery A. & Neiman, Michael L.
Partner: UNT Libraries Government Documents Department

Selective methane oxidation over promoted oxide catalysts. Quarterly report, September 1 - November 30, 1995

Description: The objective of this research is the selective oxidation of methane to C{sub 2}H{sub 4} hydrocarbons and to oxygenates, in particular formaldehyde and methanol. Air, oxygen, or carbon dioxide rather than nitrous oxide, are utilized as the oxidizing gas at high gas hourly space velocity but mild reaction conditions (500-700{degrees}C, 1 atm total pressure). All the investigated processes are catalytic, aiming at minimizing gas phase reactions that are difficult to control. During this quarter, solid state {sup 51}V NMR and double catalyst bed experiments were conducted to demonstrate the unfavorable effect of the presence of bulk crystalline V{sub 2}O{sub 5} in V{sub 2}O{sub 5}-SiO{sub 2} xerogel catalysts on selective oxidation of methane to methanol and formaldehyde. Results are discussed.
Date: December 31, 1995
Creator: Klier, Kamil; Herman, R.G. & Wang, C.B.
Partner: UNT Libraries Government Documents Department

CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

Description: A novel 1,2-ethanediol, bis(hydrogen sulfate), disodium salt precursor-based solid acid catalyst with a zirconia substrate was synthesized and demonstrated to have significantly enhanced activity and high selectivity in producing methyl isobutyl ether (MIBE) or isobutene from methanol-isobutanol mixtures. The precursor salt was synthesized and provided by Dr. T. H. Kalantar of the M.E. Pruitt Research Center, Dow Chemical Co., Midland, MI 48674. Molecular modeling of the catalyst synthesis steps and of the alcohol coupling reaction is being carried out. A representation of the methyl transfer from the surface activated methanol molecule (left) to the activated oxygen of the isobutanol molecule (right) to form an ether linkage to yield MIBE is shown.
Date: August 31, 2000
Creator: Klier, Kamil; Herman, Richard G.; Shen, James G.C. & Ma, Qisheng
Partner: UNT Libraries Government Documents Department

Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

Description: This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Brønsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.
Date: November 30, 2005
Creator: Klier, Kamil & Herman, Richard G.
Partner: UNT Libraries Government Documents Department

Oxygenates vs. synthesis gas

Description: Methanol synthesis from H{sub 2}/CO has been carried out at 7.6 MPa over zirconia-supported copper catalysts. Catalysts with nominal compositions of 10/90 mol% and 30/70 mol% Cu/ZrO{sub 2} were used in this study. Additionally, a 3 mol% cesium-doped 10/90 catalyst was prepared to study the effect of doping with heavy alkali, and this promoter greatly increased the methanol productivity. The effects of CO{sub 2} addition, water injection, reaction temperature, and H{sub 2}/C0 ratio have been investigated. Both CO{sub 2} addition to the synthesis gas and cesium doping of the catalyst promoted methanol synthesis, while inhibiting the synthesis of dimethyl ether. Injection of water, however, was found to slightly suppress methanol and dimethyl ether formation while being converted to CO{sub 2} via the water gas shift reaction over these catalysts. There was no clear correlation between copper surface area and catalyst activity. Surface analysis of the tested samples revealed that copper tended to migrate and enrich the catalyst surface. The concept of employing a double-bed reactor with a pronounced temperature gradient to enhance higher alcohol synthesis was explored, and it was found that utilization of a Cs-promoted Cu/ZnO/Cr{sub 2}O{sub 3} catalyst as a first lower temperature bed and a Cs-promoted ZnO/Cr{sub 2}O{sub 3} catalyst as a second high-temperature bed significantly promoted the productivity of 2-methyl-1-propanol (isobutanol) from H{sub 2}/CO synthesis gas mixtures. While the conversion of CO to C{sub 2+} oxygenates over the double-bed configuration was comparable to that observed over the single Cu-based catalyst, major changes in the product distribution occurred by the coupling to the zinc chromite catalyst; that is, the productivity of the C{sub 1}-C{sub 3} alcohols decreased dramatically, and 2-methyl branched alcohols were selectively formed. The desirable methanol/2-methyl oxygenate molar ratios close to 1 were obtained in the present double-bed system that provides the feedstock for the ...
Date: April 1, 1999
Creator: Klier, Kamil; Herman, Richard G.; Beretta, Alessandra; Burcham, Maria A.; Sun, Qun; Cai, Yeping et al.
Partner: UNT Libraries Government Documents Department

Mechanisms and controlling characteristics of the catalytic oxidation of methane

Description: Methane dissociation and oxygen activation have been found to be structure sensitive on different single crystal palladium surfaces. Geometrically restricted surfaces on Pd single crystal and polycrystalline surfaces using tetrachloroethylene and pentamethylcyclopentasiloxane have been formed and compared with surface structures formed using dichloromethane and chlorine. The adsorption and activation of O{sub 2}, CO, and H{sub 2}O on clean Pd surfaces and those containing the surface ensembles have also been investigated. To interpret high-resolution angle-resolved x-ray photoelectron spectra (HR AR-XPS), a new self-modeling method of resolving HR-XPS spectra was developed and applied to the experimental spectra. The effects of electron-accepting Cl, O{sub 2}, and H{sub 2}O adsobated on Cs/MoS{sub 2} were determined.
Date: July 1, 1999
Creator: Klier, Kamil; Simmons, Gary W.; Herman, Richard G.; Park, Kenneth T.; Hess, James S. & Hunsicker, Robert A.
Partner: UNT Libraries Government Documents Department

CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

Description: A tungstena-zirconia (WZ) catalyst has been investigated for coupling methanol and isobutanol to unsymmetrical ethers, i.e. methyl isobutyl ether (MIBE) and compared with earlier studied sulfated-zirconia (SZ) and Nafion-H catalysts. In all cases, the ether synthesis mechanism is a dual site S{sub N}2 process involving competitive adsorption of reactants on proximal acid sites. At low reaction temperatures, methylisobutylether (MIBE) is the predominant product. However, at temperatures >135 C the WZ catalyst is very good for dehydration of isobutanol to isobutene. The surface acid sites of the WZ catalyst and a Nafion-H catalyst were diagnosed by high resolution X-ray photoelectron spectroscopy (XPS) of N 1s shifts after adsorption of amines. Using pyridine, ethylenediamine, and triethylamine, it is shown that WZ has heterogeneous strong Broensted acid sites. Theoretical study located the transition state of the alcohol coupling reaction on proximal Broensted acid sites and accounted well for XPS core-level shifts upon surface acid-base interactions. While computations have not been carried out with WZ, it is shown that the SZ catalyst is a slightly stronger acid than CF{sub 3}SO{sub 3}H (a model for Nafion-H) by 1.3-1.4 kcal/mol. A novel sulfated zirconia catalyst having proximal strong Broensted acid sites was synthesized and shown to have significantly enhanced activity and high selectivity in producing MIBE or isobutene from methanol/isobutanol mixtures. The catalyst was prepared by anchoring 1,2-ethanediol bis(hydrogen sulfate) salt precursor onto zirconium hydroxide, followed by calcination to remove the -(CH{sub 2}CH{sub 2})- bridging residues.
Date: March 1, 2003
Creator: Klier, Kamil; Herman, Richard G.; Kwon, Heock-Hoi; Shen, James G. C.; Ma, Qisheng; Hunsicker, Robert A. et al.
Partner: UNT Libraries Government Documents Department