Wide range modeling study of dimethyl ether oxidation
01 Apr 1997-
TL;DR: A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions, such as jet-stirred reactor (JSR) at I and 10 atm, 0.2 < 0 < 2.5, and 800 < T < 1300 K.
Abstract: A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions. Experimental results obtained in a jet-stirred reactor (JSR) at I and 10 atm, 0.2 < 0 < 2.5, and 800 < T < 1300 K were modeled, in addition to those generated in a shock tube at 13 and 40 bar, 0 = 1.0 and 650 :5 T :5 1300 K. The JSR results are particularly valuable as they include concentration profiles of reactants, intermediates and products pertinent to the oxidation of DME. These data test the Idnetic model severely, as it must be able to predict the correct distribution and concentrations of intermediate and final products formed in the oxidation process. Additionally, the shock tube results are very useful, as they were taken at low temperatures and at high pressures, and thus undergo negative temperature dependence (NTC) behavior. This behavior is characteristic of the oxidation of saturated hydrocarbon fuels, (e.g. the primary reference fuels, n-heptane and iso- octane) under similar conditions. The numerical model consists of 78 chemical species and 336 chemical reactions. The thermodynamic properties of unknown species pertaining to DME oxidation were calculated using THERM.
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TL;DR: It is demonstrated that ether-based electrolytes are not suitable for rechargeable Li–O2 cells, although the ethers are more stable than the organic carbonates, the Li2O2 that forms on the first discharge is accompanied by electrolyte decomposition, to give a mixture of Li2CO3, HCO2 Li, CH3CO2Li, polyethers/ esters, CO2, and H2O.
Abstract: The rechargeable Li–air (O2) battery is receiving a great deal of interest because theoretically it can store significantly more energy than lithium ion batteries, thus potentially transforming energy storage. Since it was first described, a number of aspects of the Li–O2 battery with a non-aqueous electrolyte have been investigated. The electrolyte is recognized as one of the greatest challenges. To date, organic carbonate-based electrolytes (e.g. LiPF6 in propylene carbonate) have been widely used. However, recently, it has been shown that instead of O2 being reduced in the porous cathode to form Li2O2, as desired, discharge in organic carbonate electrolytes is associated with severe electrolyte decomposition. As a result it is very important to investigate other solvents in the search for a suitable electrolyte. In this regard much attention is now focused on electrolytes based on ethers (e.g. tetraglyme (tetraethylene glycol dimethyl ether)). Ethers are attractive for the Li–O2 battery because they are one of the few solvents that combine the following attributes: capable of operating with a lithium metal anode, stable to oxidation potentials in excess of 4.5 V versus Li/Li, safe, of low cost and, in the case of higher molecular weights, such as tetraglyme, they are of low volatility. Crucially, they are also anticipated to show greater stability towards reduced O2 species compared with organic carbonates. Herein we show that although the ethers are more stable than the organic carbonates, the Li2O2 that forms on the first discharge is accompanied by electrolyte decomposition, to give a mixture of Li2CO3, HCO2Li, CH3CO2Li, polyethers/ esters, CO2, and H2O. The extent of electrolyte degradation compared with Li2O2 formation on discharge appears to increase rapidly with cycling (that is, charging and discharging), such that after only 5 cycles there is little or no evidence of Li2O2 from powder X-ray diffraction. We show that the same decomposition products occur for linear chain lengths other than tetraglyme. In the case of cyclic ethers, such as 1,3dioxolane and 2-methyltetrahydrofuran (2-Me-THF), decomposition also occurs. For 1,3-dioxolane, decomposition forms polyethers/esters, Li2CO3, HCO2Li, and C2H4(OCO2Li)2, and for 2-Me-THF the main products are HCO2Li, CH3CO2Li; in both cases CO2 and H2O evolve. The results presented herein demonstrate that ether-based electrolytes are not suitable for rechargeable Li–O2 cells. A Li–O2 cell consisting of a lithium metal anode, an electrolyte, comprising 1m LiPF6 in tetraglyme, and a porous cathode (Super P/Kynar) was constructed as described in the Experimental Section. The cell was discharged in 1 atm O2 to 2 V. The porous cathode was then removed, washed with CH3CN, and examined by powder X-ray diffraction (PXRD) and FTIR. The results are presented in Figure 1 and Figure 2. The PXRD data demonstrate the presence of Li2O2, consistent with previous PXRD data for a Li–O2 cell with a tetraglyme electrolyte at the end of the first discharge. However, examination of the FTIR spectra, Figure 2, reveals that, in addition to Li2O2, other products form. Although the FTIR spectra provide clear evidence of electrolyte decom-
1,020 citations
TL;DR: Some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels are highlighted, which focus on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions.
Abstract: Biofuels, such as bio-ethanol, bio-butanol, and biodiesel, are of increasing interest as alternatives to petroleum-based transportation fuels because they offer the long-term promise of fuel-source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel-delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next-generation alternative fuels.
596 citations
TL;DR: A comprehensive review of the physical phenomena governing homogeneous charge compression ignition (HCCI) operation, with particular emphasis on high load conditions, is provided in this paper, with suggestions on how to inexpensively enable low emissions of all regulated emissions.
481 citations
TL;DR: In this paper, the unimolecular decomposition reaction of dimethyl ether (DME) was studied theoretically using RRKM/master equation calculations, and a hierarchical methodology was applied to produce a comprehensive high-temperature model for pyrolysis and oxidation.
Abstract: The unimolecular decomposition reaction of dimethyl ether (DME) was studied theoretically using RRKM/master equation calculations. The calculated decomposition rate is significantly different from that utilized in prior work (Fischer et al., Int J Chem Kinet 2000, 32, 713–740; Curran et al., Int J Chem Kinet 2000, 32, 741–759). DME pyrolysis experiments were performed at 980 K in a variable-pressure flow reactor at a pressure of 10 atm, a considerably higher pressure than previous validation data. Both unimolecular decomposition and radical abstraction are significant in describing DME pyrolysis, and hierarchical methodology was applied to produce a comprehensive high-temperature model for pyrolysis and oxidation that includes the new decomposition parameters and more recent small molecule/radical kinetic and thermochemical data. The high-temperature model shows improved agreement against the new pyrolysis data and the wide range of high-temperature oxidation data modeled in prior work, as well as new low-pressure burner-stabilized species profiles (Cool et al., Proc Combust Inst 2007, 31, 285–294) and laminar flame data for DME/methane mixtures (Chen et al., Proc Combust Inst 2007, 31, 1215–1222). The high-temperature model was combined with low-temperature oxidation chemistry (adopted from Fischer et al., Int J Chem Kinet 2000, 32, 713–740), with some modifications to several important reactions. The revised construct shows good agreement against high- as well as low-temperature flow reactor and jet-stirred reactor data, shock tube ignition delays, and laminar flame species as well as flame speed measurements. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 40: 1–18, 2008
435 citations
TL;DR: Dimethyl ether reaction kinetics at high temperature were studied in two different flow reactors under highly dilute conditions, with the equivalence ratio varying from 0.32 ≤ ϕ ≤ 3.4 as discussed by the authors.
Abstract: Dimethyl ether reaction kinetics at high temperature were studied in two different flow reactors under highly dilute conditions. Pyrolysis of dimethyl ether was studied in a variable-pressure flow reactor at 2.5 atm and 1118 K. Studies were also conducted in an atmospheric pressure flow reactor at about 1085 K. These experiments included trace-oxygen-assisted pyrolysis, as well as full oxidation experiments, with the equivalence ratio (ϕ) varying from 0.32 ≤ ϕ ≤ 3.4. On-line, continuous, extractive sampling in conjunction with Fourier Transform Infra-Red, Non-Dispersive Infra-Red (for CO and CO2) and electrochemical (for O2) analyses were performed to quantify species at specific locations along the axis of the turbulent flow reactors. Species concentrations were correlated against residence time in the reactor and species evolution profiles were compared to the predictions of a previously published detailed kinetic mechanism. Some changes were made to the model in order to improve agreement with the present experimental data. However, the revised model continues to reproduce previously reported high-temperature jet-stirred reactor and shock tube results. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet: 32: 713–740, 2000
400 citations
References
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TL;DR: In this paper, the authors present a compilation of critically evaluated kinetic data on elementary homogeneous gas phase chemical reactions for use in modelling combustion processes Data sheets are presented for some 196 reactions each data sheet sets out relevant thermodynamic data, rate coefficient measurements, an assessment of the reliability of the data, references and recommended rate parameters Tables summarizing the preferred rate data are also given
Abstract: This compilation contains critically evaluated kinetic data on elementary homogeneous gas phase chemical reactions for use in modelling combustion processes Data sheets are presented for some 196 reactions Each data sheet sets out relevant thermodynamic data, rate coefficient measurements, an assessment of the reliability of the data, references, and recommended rate parameters Tables summarizing the preferred rate data are also given The reactions considered are limited largely to those involved in the combustion of methane and ethane in air but a few reactions relevant to the chemistry of exhaust gases and to the combustion of aromatic compounds are also included
1,986 citations
TL;DR: It is demonstrated that ether-based electrolytes are not suitable for rechargeable Li–O2 cells, although the ethers are more stable than the organic carbonates, the Li2O2 that forms on the first discharge is accompanied by electrolyte decomposition, to give a mixture of Li2CO3, HCO2 Li, CH3CO2Li, polyethers/ esters, CO2, and H2O.
Abstract: The rechargeable Li–air (O2) battery is receiving a great deal of interest because theoretically it can store significantly more energy than lithium ion batteries, thus potentially transforming energy storage. Since it was first described, a number of aspects of the Li–O2 battery with a non-aqueous electrolyte have been investigated. The electrolyte is recognized as one of the greatest challenges. To date, organic carbonate-based electrolytes (e.g. LiPF6 in propylene carbonate) have been widely used. However, recently, it has been shown that instead of O2 being reduced in the porous cathode to form Li2O2, as desired, discharge in organic carbonate electrolytes is associated with severe electrolyte decomposition. As a result it is very important to investigate other solvents in the search for a suitable electrolyte. In this regard much attention is now focused on electrolytes based on ethers (e.g. tetraglyme (tetraethylene glycol dimethyl ether)). Ethers are attractive for the Li–O2 battery because they are one of the few solvents that combine the following attributes: capable of operating with a lithium metal anode, stable to oxidation potentials in excess of 4.5 V versus Li/Li, safe, of low cost and, in the case of higher molecular weights, such as tetraglyme, they are of low volatility. Crucially, they are also anticipated to show greater stability towards reduced O2 species compared with organic carbonates. Herein we show that although the ethers are more stable than the organic carbonates, the Li2O2 that forms on the first discharge is accompanied by electrolyte decomposition, to give a mixture of Li2CO3, HCO2Li, CH3CO2Li, polyethers/ esters, CO2, and H2O. The extent of electrolyte degradation compared with Li2O2 formation on discharge appears to increase rapidly with cycling (that is, charging and discharging), such that after only 5 cycles there is little or no evidence of Li2O2 from powder X-ray diffraction. We show that the same decomposition products occur for linear chain lengths other than tetraglyme. In the case of cyclic ethers, such as 1,3dioxolane and 2-methyltetrahydrofuran (2-Me-THF), decomposition also occurs. For 1,3-dioxolane, decomposition forms polyethers/esters, Li2CO3, HCO2Li, and C2H4(OCO2Li)2, and for 2-Me-THF the main products are HCO2Li, CH3CO2Li; in both cases CO2 and H2O evolve. The results presented herein demonstrate that ether-based electrolytes are not suitable for rechargeable Li–O2 cells. A Li–O2 cell consisting of a lithium metal anode, an electrolyte, comprising 1m LiPF6 in tetraglyme, and a porous cathode (Super P/Kynar) was constructed as described in the Experimental Section. The cell was discharged in 1 atm O2 to 2 V. The porous cathode was then removed, washed with CH3CN, and examined by powder X-ray diffraction (PXRD) and FTIR. The results are presented in Figure 1 and Figure 2. The PXRD data demonstrate the presence of Li2O2, consistent with previous PXRD data for a Li–O2 cell with a tetraglyme electrolyte at the end of the first discharge. However, examination of the FTIR spectra, Figure 2, reveals that, in addition to Li2O2, other products form. Although the FTIR spectra provide clear evidence of electrolyte decom-
1,020 citations
TL;DR: Some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels are highlighted, which focus on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions.
Abstract: Biofuels, such as bio-ethanol, bio-butanol, and biodiesel, are of increasing interest as alternatives to petroleum-based transportation fuels because they offer the long-term promise of fuel-source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel-delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next-generation alternative fuels.
596 citations
TL;DR: THERM as discussed by the authors is a computer code for an IBM PC/XT/AT or compatible which can be used to estimate, edit, or enter thermodynamic property data for gas phase radicals and molecules using Benson's group additivity method.
Abstract: We have developed a computer code for an IBM PC/XT/AT or compatible which can be used to estimate, edit, or enter thermodynamic property data for gas phase radicals and molecules using Benson's group additivity method. The computer code is called THERM (THermo Estimation for Radicals and Molecules). All group contributions considered for a species are recorded and thermodynamic properties are generated in old NASA polynomial format for compatibility with the CHEMKIN reaction modeling code. In addition, listings are created in a format more convenient for thermodynamic, kinetic, and equilibrium calculations. Polynomial coefficients are valid from 300–5000 K using extrapolation methods based upon the harmonic oscillator model, an exponential function, or the Wilhoit polynomials. Properties for radical and biradical species are calculated by applying bond dissociation increments to a stable parent molecule to reflect loss of H atom. THERM contains a chemical reaction interpreter to calculate thermodynamic property changes for chemical reactions as functions of temperature. These include equilibrium constant, heat release (required heat, ΔHr), entropy change (ΔSr), Gibbs free energy change (ΔGr), and the ratio of forward to reverse Arrhenius A-factors (for elementary reactions). This interpreter can also process CHEMKIN input files. A recalculation procedure is incorporated for rapid updating of a database of chemical species to reflect changes in estimated bond dissociation energies, heats of formation, or other group values. All input and output files are in ASCII so that they can be easily edited, expanded, or updated.
483 citations
TL;DR: A comprehensive review of the physical phenomena governing homogeneous charge compression ignition (HCCI) operation, with particular emphasis on high load conditions, is provided in this paper, with suggestions on how to inexpensively enable low emissions of all regulated emissions.
481 citations