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Title: Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

Abstract

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 Brnsted 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 themore » 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.« less

Authors:
;
Publication Date:
Research Org.:
Lehigh University
Sponsoring Org.:
USDOE - Office of Energy Research (ER)
OSTI Identifier:
860951
Report Number(s):
DOE/ER/15181-F
TRN: US200721%%725
DOE Contract Number:
FG02-01ER15181
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALCOHOLS; AROMATICS; BROENSTED ACIDS; CARBOXYLIC ACIDS; CATALYSTS; CHEMICAL PROPERTIES; ESTERS; ETHERS; FASTENING; LIQUID FUELS; MONOMERS; NATURAL GAS; OCTANE; OXIDES; REACTION KINETICS; SULFATES; SURFACE AREA; SYNTHESIS; Alcohols, Ethers, Alternative Fuels, Catalysis, Catalysts, Catalytic Processes, Fossil Energy, Chemical Transformations

Citation Formats

Klier, Kamil, and Herman, Richard G. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics. United States: N. p., 2005. Web. doi:10.2172/860951.
Klier, Kamil, & Herman, Richard G. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics. United States. doi:10.2172/860951.
Klier, Kamil, and Herman, Richard G. Wed . "Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics". United States. doi:10.2172/860951. https://www.osti.gov/servlets/purl/860951.
@article{osti_860951,
title = {Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics},
author = {Klier, Kamil and Herman, Richard G},
abstractNote = {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 Brnsted 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.},
doi = {10.2172/860951},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Nov 30 00:00:00 EST 2005},
month = {Wed Nov 30 00:00:00 EST 2005}
}

Technical Report:

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  • The interaction of oxygen with Pd(100) single crystal surfaces was studied with the objective of determining the mechanisms, the most suitable metallic catalyst, and the most favorable conditions for the oxidation and partial oxidation of methane. The various adsorbed oxygen phases p(2 {times} 2), 0.25ML; c(2 {times} 2), 0.50 ML; p(5 {times} 5), 0.68 ML; and ({radical}5x{radical}5)R27{degree}, 0.80 ML were produced under conditions of oxygen pressure and surface temperatures that has led to the refinement of the phase diagram for this system. In addition, novel interpretations of the surface structures, surface vibrational spectra, and thermal desorption spectra are offered.
  • The objective of this research is the development of the fundamental knowledge of the catalytic function of transition metals (Pd and Rh) in conversion of methane to oxygenates and C/sub 2//sup +/ hydrocarbons, which will lead to new catalysts for these processes. Since oxygen chemisorbed on palladium effects the oxidation of methane under mild conditions, all of the oxygen phases that formed on Pd(100) for oxygen pressures of 1.3 x 10/sup -9/ kPa to 1.3 x 10/sup -7/ kPa and temperatures of 300K to 600K were characterized. Oxygen was found to adsorb dissociatively and to form a sequence of orderedmore » structures with increasing coverage. During the past year, a needle doser has been constructed in our stainless steel ultra-high vacuum (UHV) chamber, and it has been used to study the reaction of methane with the following surfaces: Clean Pd(100), O/Pd(100), Cl/Pd(100), and O/Cl/Pd(100). 12 refs., 1 fig., 2 tabs.« less
  • 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,more » O{sub 2}, and H{sub 2}O adsobated on Cs/MoS{sub 2} were determined.« less
  • Progress has included (1) construction and installation of an ultraviolet photoelectron spectrometer (UPS) with power supply and pumping system that has been added as an attachment to the SCIENTA ESCA-300 instrument, (2) modification of the high resolution electron energy loss spectrometer (HREELS) to produce a stable ultra high vacuum (UHV) environment for initial experiments with a Pd(311) single crystal, (3) construction of a separate high vacuum system for preparation of surface doped model catalysts by chemical vapor deposition and pretreatment of a Pd(100) single crystal in this system, (4) carried out detailed experiments of methane activation and oxidation on Pd(679)more » using a high pressure reaction cell contained in a third ultra high vacuum system, (5) completion of adsorption/desorption studies of H{sub 2}, CO, and O{sub 2} on Pd(679), (6) utilized angle-resolved XPS to probe the diffraction characteristics and structure of the Pd(100) surface, (7) determination of the electronic surface structure of Pd(100) using angle-resolved UPS, and (8) computational analysis of oxygen overlayers on the PD(100) surface. Each of these is discussed in further detail below.« less
  • The objective of the proposed research is to develop new ways to control the catalytic and selective oxidation of methane to oxygenates other then CO{sub 2} under mild reaction conditions by using halogen-free surface species that are stable under reaction conditions and that control the size of palladium ensembles available chemisorption of methane and oxygen. This will ensure the absence of Cl-containing products in the product and will result in surface modifiers, e.g. palladium alloy moieties, that are more stable at higher temperatures than are CCl{sub 2}- and Cl-produced site blocking agents. The model catalysts being utilized are initially singlemore » crystals of planar Pd(100), stepped Pd(311), and stepped and kinked Pd(679), which will also provide for the structure sensitivity of the selective oxidation of CH{sub 4} to be probed. 6 refs., 1 fig.« less