Engineering topics

McCormick, Robert (ORCID:0000000314627165)

Publications and source records attributed to McCormick, Robert (ORCID:0000000314627165).

3 records

DOE OSTI2024

An experimental and chemical kinetic modeling study of 4-butoxyheptane combustion

Here, the combustion kinetics of a novel oxygenated bioblendstock for diesel, 4-butoxyheptane (4-BH), was investigated experimentally using a flow reactor and a heated, high-pressure shock tube. The flow reactor experiments employed oxygen as the oxidizer and helium as the diluent with oxidation conducted at atmospheric pressure and 10 bar for temperatures from 400 to 1000 K at 20-K intervals. The fuel, oxidizer, and diluent flow rates were varied at different temperatures to maintain a constant initial fuel mole fraction of 1000 ppm, with stoichiometric equivalence ratio, and a residence time of 2.0 s. The reacted gas was fed to two separate GC systems that could qualitatively and quantitatively detect product species. Additionally, real fuel-air ignition delay time (IDT) data were collected using a heated, high-pressure shock-tube facility. Fuel lean (φ = 0.5) and stoichiometric (φ = 1.0) mixtures were investigated at 10 atm as well as at 30 atm for the fuel lean case for temperatures between 847 and 1259 K. A detailed chemical kinetics mechanism was developed to model the product distribution from the flow reactor and IDTs from the shock tube. The proposed model was able to predict the double NTC behavior in flow reactor experiments reasonably well. Model predictions at low temperatures were observed to be highly sensitive to the rate constants of ketohydroperoxide (KHP) decomposition in the case of the OOH group in α position which were modeled based on existing literature studies on ethers. It was noted that in the absence of theoretical or experimental studies, the rate constants for KHP decomposition used in the literature were empirically set. Additional studies are required to address the gap in model prediction obtained in this study and to reduce the uncertainty in kinetics models for ether oxidation. Predicted product concentrations and IDTs showed some quantitative agreement with experimental data, but the overall reactivity of the IDTs is underpredicted. Additionally, significant deviation is observed for the IDT results at 10 atm for the stoichiometric case with minor deviations for the other cases. The reaction pathways to the missing products were then further analyzed theoretically through quantum-mechanical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Diesel Oxidation Catalyst Performance with Biodiesel Formulations

Biodiesel (i.e., mono-alkyl esters of long chain fatty acids derived from vegetable oils and animal fats) is a renewable diesel fuel providing life-cycle greenhouse gas emission reductions relative to petroleum-derived diesel. With the expectation that there would be widespread use of biodiesel as a substitute for ultra-low sulfur diesel (ULSD), there have been many studies looking into the effects of biodiesel on engine and aftertreatment, particularly its compatibility to the current aftertreatment technologies. The objective of this study was to generate experimental data to measure the effectiveness of a current technology diesel oxidation catalysts (DOC) to oxidize soy-based biodiesel at various blend levels with ULSD. Biodiesel blends from 0 to 100% were evaluated on an engine using a conventional DOC. In the steady-state performance test where fuel dosing rate was increased at fixed DOC inlet temperature, B20 performed similarly to ULSD at the lowest flow rate or exhaust temperature over 340 degrees C for medium and high flows. B50 blends performed nearly as well under most conditions. Higher blends exhibited reduced thermal efficiency and DOC outlet temperature with increasing dosing rate under most conditions and required exhaust temperatures over 400 degrees C to achieve or nearly achieve performance similar to ULSD. In the steady-state light of test where fuel dosing rate is fixed but exhaust temperature is increased incrementally, B20 generally performed similarly to ULSD at the highest inlet temperature, with only minor deficiencies at lower temperatures. Higher blends exhibited lower thermal efficiency and did not achieve as high DOC outlet temperatures. In the transient light-off test light-off temperature for ULSD was typically less than 225 degrees C, while for B100 it ranged from 290 degrees C to 330 degrees C. Based on the data set, it can be concluded that biodiesel fuels have a higher light-off temperature primarily because of their higher boiling points, with a minor secondary impact of their lower energy content.

ADVANCED PROPULSION SYSTEMS,BIOMASS FUELS↗

DOE OSTI2023

Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

One of the major biofuels used today is biodiesel, composed of fatty acid methyl esters. The fats and oils feedstocks used to make biodiesel are in relatively short supply. To meet increasing global demand, engineered microorganisms have been developed to catalyze conversion of sugar to fatty acid esters that contain unique ..beta..-hydroxy-esters. This study investigated the effect of a hydroxyl group on the combustion characteristics of methyl esters by comparing the chemical behavior of methyl hexanoate (MHx) and methyl 3-hydroxyhexanoate (M3OHHx) - used as surrogates for diesel-boiling-range esters with longer fatty acid chains. The oxidation of these esters was studied experimentally in a flow reactor at 0.84 and 10 bar, 600 to 1,100 K, and stoichiometric conditions; and in a constant volume combustion chamber at 5 and 10 bar, 600 to 900 K, and equivalence ratios of 0.3 and 0.6. MHx was more reactive in the constant volume chamber at temperatures below 800 K at 10 bar and equivalence ratio of 0.6. MHx also exhibited a higher indicated cetane number (16.4) than M3OHHx (8.1). We investigated this reactivity trend using an updated MHx kinetic model and M3OHHx model developed as part of this work. The kinetic models predicted that radicals formed from MHx were consumed by low-temperature chemistry reactions, whereas the M3OHHx reactivity was significantly governed by the ..beta..-radical (on the same carbon as the OH group) chemistry which mainly terminated via the less reactive chain propagation pathway to methyl-3-oxohexanoate + HO2. This study extends our understanding of structural effects on ester reactivity, which will allow for accurate surrogate formulation and performance simulations.

AFIDA↗