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DOE OSTI2024

Data assimilation for combustion ignition delay time simulation using schlieren image velocimetry

This study sought to improve the accuracy of simulating spray penetration and combustion ignition delay by means of data assimilation (DA). The simulations were conducted using the Reynolds-averaged Navier–Stokes (RANS) equations and assimilating the schlieren image data. In DA, an ensemble square root filter (EnSRF) was used to build the statistical model, making the simulation results more accurate without any change in the governing equations. Recognizing that the spray-cone injection angle has a large effect on penetration, we created ensemble members with different injection angles. And we applied the two-component velocity distribution calculated via SIV and updated both velocity and temperature by using a DA statistical model derived from RANS ensemble simulations. The ignition delay time is generally known to vary even under the same experimental conditions because it is influenced by many factors. In this study, we attempted the transient DA-assisted RANS simulation to predict the ignition delay time even when the temporal resolution and accuracy of the observation data ware insufficient. Our trials offer an example of how a combination of techniques can be effectively used to assimilate experimental data obtained under restricted conditions.

Combustion simulation↗

DOE OSTI2025

Measurement of Spray Chamber Ignition Delay and Cetane Numbers for Aviation Turbine Fuels

Experiments using pure compounds, National Jet Fuels Combustion Program (NJFCP) test fuels, and commercial jet fuels were conducted to demonstrate the equivalence of the indicated cetane number (ICN) and derived cetane number (DCN) for jet fuels. The calibrated range for ICN was also extended to lower cetane number (CN) values (5 to 35) to allow CN quantification for jet fuel synthetic blending components (SBCs) with low CN. ICN and DCN were shown to be highly correlated for values above about 30. This study presents the most comprehensive comparison of these two methods published to date. Because of the importance of low-volume test methods for early-stage SBC production process development, we demonstrated that ICN and DCN can be accurately measured with 15 mL of fuel, well below 40 to 100 mL required by standard methods. ICN or DCN is important for jet fuels because fuels with lower CN are more prone to lean blowout (LBO), an undesirable operational failure in a jet engine. Comparing data on a fuel-to-air ratio (Φ) at LBO for the NJFCP fuels shows similar linear correlations for ICN and DCN. Ignition delay measurements at lower-pressure and higher-temperature conditions may be more directly relevant to LBO. At 675 °C, 0.5 MPa, and a global Φ of roughly 0.68, ignition delay time correlations to LBO were similar to those produced from DCN and ICN. A much weaker correlation was obtained with a global Φ value of 0.34.

09 BIOMASS FUELS↗

DOE OSTI2026

Probability of Hydrogen Ignition: A Landscape Review and Gaps Assessment

The primary hazard of a leak from a hydrogen system is due to the immediate or delayed ignition of the fuel leading to a jet flame or explosion. Therefore, understanding the hydrogen ignition probability is critical for analyzing the risk of hydrogen systems. This report reviews the current understanding of hydrogen ignition mechanisms and methods for modeling their probability. The stoichiometry, ignition strength, and ignition source temperature are all important characteristics that can affect both the probability of ignition and the outcome of the subsequent combustion event. A brief review of diffusion ignition demonstrates that ignition probability models must account for seemingly spontaneous ignition of hydrogen in addition to scenarios where the ignition source is readily identified. State-of-the art models for both immediate and delayed ignition probabilities are presented, including different physical aspects of the scenarios (e.g., flow rate, ignition source characteristics) that are considered in the different modeling approaches. Current models often fail to account for the unique properties of hydrogen compared to other fuels, and most lack rigorous validation with hydrogen as a fuel. A fault tree framework is proposed to systematically evaluate the probability of ignition by integrating various ignition mechanisms and their uncertainties. Furthermore, this type of framework could enable additional insights into the most important mechanisms and would enable uncertainty quantification in risk assessment modeling. Recommendations for future research include the need for experimental validation of ignition models and the development of comprehensive methodologies that incorporate the specifics of hydrogen behavior in real-world scenarios.

hydrogen↗

DOE OSTI2025

DME-Propane Blends Ignition Experiments and Modeling for Heavy-Duty Mixing Controlled Compression Engines

A blend of dimethyl ether (DME) and propane (C3H8) is being studied in a shock tube at heavy-duty engine conditions at 110 bar. Due to its intrinsic combustion properties, DME/propane blend can potentially replace diesel in mixing controlled compression ignition engines. A blend of DME/propane can reduce emissions in mixing controlled compression ignition in heavy-duty engines through modifications, which require simulations using a high-fidelity chemical kinetics model that can accurately predict the chemistry of the blend. An essential aspect of testing the chemical kinetics model is doing baseline fundamental chemistry studies on neat DME and propane, which include ignition delay time measurements. In this work, using a high-pressure shock tube, ignition delay times were gathered for DME/Propane blends at 110 bar diluted with AR to test chemical kinetic models published in the literature. These models include Aramco 3.0, NUIG V1.1, C3mech V3.3, and Dames et al. Comparisons with the experimental IDTs and models were conducted, and general agreement was observed. A sensitivity analysis was conducted, and important reactions were outlined.

Mohammed, Zuhayr Pasha [University of Central Flor↗

DOE OSTI2024

SHOCK TUBE IGNITION STUDIES OF RENEWABLE DIESEL FUELS FOR MEDIUM AND HEAVY-DUTY TRANSPORTATION

Currently extensive research on alternative fuels is being conducted due to their increasing demand to reduce greenhouse emissions. One renewable fuel studied in this work is dimethyl ether (DME) blended with propane(C3H8) as a potential mixture for heavy-duty engines used in semi-trucks. The blend has the potential to drastically reduce particulate and greenhouse gas emissions compared to a conventional diesel engine operating under similar conditions. To develop the use of mixture, one must conduct detailed conceptual and simulation studies before progressing to detail studies in CFD, engine modifications, and live testing. For simulations, accurate high-fidelity chemical kinetic models are necessary. However, the validity of the chemical kinetic mechanism for operating conditions of a heavy-duty mixing-controlled compression (MCCI) engine was widely unknown until recent work presented here and published. In this work, we studied the ignition of DME and propane blends in a shock tube under MCCI engine conditions. Ignition delay time (IDT) gathered behind the reflected shock for DME-propane mixtures for heavy-duty compression ignition (CI) engine parameters. Testing was conducted for undiluted varieties spanning from temperatures of 700 to 1100 K at pressures ranging from 55 to 84 bar for various blends (100% CH3OCH3, 100% C3H8, 60% CH3OCH3/ 40% C3H8) of DME and propane were combusted in synthetic air (21% O2/ 79% N2). Several experiments were conducted at higher pressures (90-120 bar) to improve the model performance and accuracy. The ignition delay times (IDTs) were compared to recent mechanisms, including Aramco3.0, NUIG, and Dames et al. A common trend among the mechanisms was overpredicted experimental IDTs. Further studies were conducted by a sensitivity analysis using the Dames et al. model, and critical reactions sensitive to IDTs of DME-propane mixture near 60 bar are outlined. Chemical analysis was conducted on the NTC region to explain chemical kinetics which is critical for developing MCCI heavy duty engines.

Mohammed, Zuhayr Pasha↗

DOE OSTI2025

AUTOIGNITION DELAY TIMES FOR REFORMATE GAS MIXTURES FROM METHANE GAS ENGINES

Methane slip is a prominent issue in natural gas reciprocating engines that are used in transportation and marine applications. The incomplete combustion that results in methane slip can be resolved with the introduction of hydrogen within the combustion mixture to improve methane oxidation and further enable combustion within the engine crevices where methane has previously remained unreacted. Steam methane reforming (SMR) is a common method used to produce hydrogen and can be used to design an onboard device to reduce methane slip from reciprocating engines. The development of this reformer device requires the validation of high-fidelity chemical kinetic models at the low temperatures of the crevice volumes of these engines. In this work, auto-ignition data is obtained using a shock tube at lean (φ—0.714 or λ—1.4) and stoichiometric (φ, λ = 1) equivalence ratios spanning a temperature range of 1042–1234 K at the 80-bar operating pressure of the test engine. Blends of methane, hydrogen, and reformate products from the SMR reaction are shock-heated in synthetic air, with the ignition delay time measured using an OH* chemiluminescence detector at 310 nm and a CH* detector at 430 nm. The experimental results are compared to several state-of-the-art chemical kinetic mechanisms from the literature. In general, most of the mechanisms show very good agreement with experiments at higher temperatures, with simulation results showing little deviation from experiments at lower temperatures. A sensitivity analysis was conducted, and the results reveal that the reaction H2 + CH3O2 = H + CH3O2H has a very significant role in determining low-temperature ignition delay times (IDTs) of SMR mixtures. These findings provide valuable insights into the chemical kinetics governing methane reformate combustion and contribute to the optimization of onboard reformer designs aimed at mitigating methane slip in natural gas-fueled engines.

Fraze, Matthew↗

DOE OSTI2025

Dual-Fuel Ammonia Equivalence Ratio Sweep Data

Ammonia (NH3) has garnered significant interest as an alternative fuel for meeting international emissions reduction mandates in sectors with high weight and distance requirements, such as shipping. Technical barriers and unanswered questions remain on the combustion strategies that can maximize ammonia utilization and minimize emissions. Prior research studies at the US Department of Energy’s Oak Ridge National Laboratory have shown strong performance with NH3 under dual-fuel mode using conventional diesel combustion (CDC) manifold air pressure settings. Diesel airflow was initially used to simplify retrofitting (no turbocharger modification), which resulted in air-fuel equivalence ratios (λ) greater than 1.5. To characterize potential improvements in dual-fuel NH3 combustion performance at richer in-cylinder conditions, a global λ sweep compared the use of early (E-pilot) and late (L-pilot) single diesel injections. The experiments were conducted at 1200 RPM and 12.8 ± 0.2 bar (75 % load), and λ was varied by decreasing the commanded air flow to the engine at greater than 90 % ammonia energy substitution level. A diesel injection timing sweep was conducted for both the injection strategies at fixed λ, and the timing with the lowest engine-out N2O emissions was identified. The results indicated an optimal balance between CO2,eq and thermal efficiency benefits both E-pilot and L-pilot injection strategy cases compared with CDC at a λ of 1.4. The indicated nitrogen-based emissions exhibited a strong correlation to the ratio of CA5–50 and ignition delay for L-pilot, but no apparent trend emerged for the E-pilot injection strategy at the tested boundary conditions. This dataset includes the raw experimental data and documentation of the experiment conditions and methods.

30 DIRECT ENERGY CONVERSION↗

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 OSTI2025

Numerical Investigation of Ammonia/n-Heptane Dual-Fuel Spray Flames Using Large Eddy Simulations

Diesel engines are extensively used in heavy-duty transportation, power generation, and marine vehicles due to their superior thermal efficiency and extended high-load operability compared to spark ignition (SI) engines. However, combustion in diesel engines is generally characterized by locally rich fuel–air mixtures and high combustion temperatures, causing significant amounts of soot and NO x emissions from these engines. Utilizing carbon-free alternative fuels and enhancing fuel efficiency represent promising strategies to mitigate greenhouse gas (GHG) and other emissions in the heavy-duty transportation sector. In this context, ammonia (NH 3 ), as a hydrogen carrier, has received significant attention as a viable substitute for hydrocarbon fuels due to its carbon-free composition, relatively high energy density, and well-established infrastructure. Many previous studies have considered combustion and emission characteristics of ammonia-hydrocarbon fuel blends in engines and simplified flames. But, detailed investigations on the effects of ammonia on the performance of hydrocarbon fuels under engine conditions are lacking. In the present study, we perform large eddy simulations (LES) of the ignition and flame processes in a constant-volume combustion reactor, where n-heptane is injected in an ammonia/air ambient mixture in a diesel-like environment. A detailed and validated reaction mechanism containing 302 species and 1981 reactions is employed. The Engine Combustion Network Spray H experimental data is used to validate the spray model under both non-reacting and reacting conditions. Dual-fuel combustion is simulated using the well-stirred reactor (WSR) approach. Results are presented for two spray cases: (1) single fuel (SF) with n-heptane injected into a mixture of air and combustion products and (2) dual-fuel (DF) with the injection of n-heptane in a mixture of air, ammonia, and combustion products. It is observed that the presence of ammonia has a significant effect on the ignition and flame development processes. With ammonia addition, both the first- and second-stage ignition delay times increase, but the effect of ammonia on the second-stage ignition is significantly more prominent. In addition, the ignition kernel size and growth rate decrease noticeably. For SF spray, the main ignition is characterized by multiple ignition kernels near the spray tip, whereas for DF spray, a single relatively small ignition kernel forms and grows slowly in the downstream direction. The flame development and the final quasi-steady flame structure are also modified due to ammonia. Here, the outcome of this research would enable a better understanding of ammonia–diesel dual-fuel spray flame behavior and guide the development of associated engine combustion strategies.

ammonia↗

DOE OSTI2026

An experimental and kinetic modeling study of the ignition of 2-methyl decane

Ignition delay times (IDTs) of 2-methyl decane (C 11 H 24 -2) are measured in a high-pressure shock tube and in a rapid compression machine at equivalence ratios in the range 0.5–2.0 at 90 % dilution, at temperatures in the range 600–1430 K and at pressures of 15 and 30 bar. To clarify the effect of the branched methyl group on fuel oxidation, IDTs of n-undecane (nC 11 H 24 ) are also measured at similar conditions to those measured for C 11 H 24 -2. A new chemical kinetic mechanism, using C3MechV4.0.1 as the core chemistry, is developed and validated against the new experimental data. The thermodynamic properties of the fuel (RH), alkyl (Ṙ), alkyl peroxy (RȮ 2 ), hydroperoxy-alkyl (Q̇OOH), and peroxy hydroperoxy alkyl (Ȯ 2 QOOH) radicals are updated in both the C 11 H 24 -2 and nC 11 H24 models using THERM25. A reaction path flux analysis for C 11 H 24 -2 at different temperatures was conducted. Compared to nC 11 H 24 , C 11 H 24 -2 shows slower reactivity. At low and intermediate temperatures, the chain propagation pathway Q̇OOH ↔ C 11 cyclic ether + ȮH is favored for C 11 H 24 -2, while the chain branching pathway Q̇OOH ↔ Ȯ 2 QOOH ↔ C 11 carbonyl hydroperoxide (KHP) + ȮH is suppressed, leading to lower reactivity compared to nC 11 H 24 . At high temperatures, the presence of the branched methyl group inhibits the direct decomposition of the fuel, resulting in reduced C 2 H 4 formation, which in turn suppresses the reactivity of the fuel.

2-methyl decane↗

DOE OSTI2026

Prioritizing Uncertainties in Hydrogen Contribution to Risk in Post-Crash Outcomes for Rail

This report presents analysis from Sandia National Laboratories predicting contributions to risk associated with the use of hydrogen technology for rail. Event sequence diagrams are used to describe possible accident scenarios and progressions. Initiating event frequencies and branch event probabilities for each scenario are quantified with uncertainty using distributions fit to Federal Railroad Administration and U.S. Department of Transportation Pipeline and Hazardous Materials Safety Administration data on applicable accidents from 2000 to 2020. Uncertainty is propagated through the event sequence diagram to estimate the frequency and conditional probability of accident end states. The analysis identifies four scenarios with significant contributions to risk from hydrogen that are predicted to occur relatively frequently, which may inform priorities for reducing uncertainty. These scenarios are 1) overpressure events resulting from collisions with hydrogen release due to mechanical damage and delayed ignition, 2) jet fire events resulting from collisions with hydrogen release due to mechanical damage and immediate ignition, 3) jet fires resulting from fire or explosion initiating events involving the hydrogen tank and correct operation of the thermally-activated pressure relief device (TPRD) subsequent to the thermal insult, and 4) pressure burst resulting from fire or explosion initiating events involving the hydrogen tank and failure of the TPRD. Delayed and immediate hydrogen ignition probabilities are identified as being highly uncertain and potential candidates for reducing conservatism in the predicted frequencies for these two scenarios.

08 HYDROGEN↗

DOE OSTI2025

Co-optimization of fuel properties, combustion system geometry, and injection strategy for conventional diesel fuel

Here, studies have shown that fuel properties can impact an engine’s operation in several ways, including ignition delay, sooting tendency, mixture formation, and combustion temperature. In mixing-controlled compression ignition (MCCI) engines, the fuel system design and piston bowl geometry significantly affect combustion performance and emissions. Based on current information, it is difficult to draw conclusions about fuel property effects and sensitivities. The central fuel hypothesis approach used in the US Department of Energy Co-Optima program has worked well for spark ignition fuels: identifying critical fuel property ranges is sufficient to screen fuel blends that are expected to maximize efficiency and reduce pollutant emissions. However, for MCCI-relevant fuels, the information gained from past studies is not sufficient to build such a merit function or to allow for performing a similar screening of fuel blends. It is hypothesized that a co-optimization of a fuel’s physical and chemical properties, combustion system geometry, and injection strategy could leverage synergies between the effects of the fuel properties and geometries, resulting in improved performance over state-of-the-art. A machine learning–assisted unconstrained global optimization algorithm was used to explore a design space comprising 23 independent variables. The results show that physical property effects were minimal even for large variations in fuel properties, and the only interaction effect that was observed was the effect of varied fuel density parameters on fuel/air mixture formation. Nevertheless, these interactions were not sufficient in magnitude to significantly affect optimization results. Therefore, analysis of the results suggests that fuel physical properties cannot be leveraged in a co-optimization context to increase engine efficiency.

33 ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2026

A single-zone zero-dimensional study of HCCI combustion of methanol dehydration products to enable ignition of direct-injected methanol

Methanol is an alternative fuel gaining traction in the maritime sector. Its direct adoption, however, is accompanied by a unique set of technical challenges, such as low cetane number and high latent heat of vaporization. An approach to overcome these challenges is being developed at the US Department of Energy’s Oak Ridge National Laboratory, where onboard generation of dimethyl ether (DME) via catalytic dehydration of methanol can be used to assist in the mixing controlled combustion of direct-injected (DI) methanol. The generated mixture from this dehydration process can be premixed with intake air to condition the cylinder via. homogeneous charge compression ignition (HCCI) for subsequent DI methanol. In this preliminary work, various catalyst or reactor conversion efficiencies were simulated (using bottles) at constant DME and water flow at low load on a single-cylinder marine-variant of a CAT® C18 18 L engine with a 145 mm bore. To substantiate the experimental findings, a zero-dimensional engine model was developed in Cantera using a DME mechanism with 79 species and 658 reactions. Results presented include experimental and simulation heat release rate comparisons, species evolution information, and constant volume ignition delay (ID) for DI methanol with and without background species from HCCI of the premixed products from different reactor efficiencies. The results suggest that thermal effects dominate the DI methanol ignition process, and this work provides a chemical kinetic foundation or guideline for developing future control schemes.

Tyrewala, Daanish [ORNL] (ORCID:0000000208599324)↗

DOE OSTI2026

Modeling the Effects of Trimethylsilanol on Syngas Combustion Kinetics

A perturbation analysis modeling approach based on a genetic algorithm was used to identify possible reaction pathways to explain previous experimental observations of the strong acceleration of syngas auto-ignition by trimethylsilanol (TMSO). Organosilicon reactions were taken from an existing chemical kinetic mechanism for tetramethylsilane pyrolysis which also contained TMSO reactions. The experimental targets for optimization were ignition delay times and peak OH radical concentrations in the range 1010–1070 K, 5 atm with dilute (4%) ϕ = 0.1 syngas mixtures in N 2 /Ar containing 0, 200, and 1000 ppm TMSO. Hundreds of thousands of trials resulted in three models which accurately predicted the experimental auto-ignition times and peak OH concentrations. Rate of production analyses indicated that TMSO forms dimethylsilanediol, which then reacts creating two “catalytic loops.” The net effect of the loops is to accelerate the reaction H 2 + O = OH + H at a faster effective rate than H 2 /O 2 kinetics alone, thus enhancing the reactivity of syngas. The formation of the loops may be attributable to the high Si–C bond energies in siloxanols, reducing rates of thermal decomposition and allowing dimethylsilanediol to react with H 2 for a longer duration compared with its alkane analog. Here, the results of the current work provide valuable direction for fundamental studies of these new hypothesized reaction pathways.

Mansfield, Andrew B. [Eastern Michigan University,↗

DOE OSTI2024

Asynchronicity in opposed-piston RCMs: Does it matter?

Rapid Compression Machines (RCMs) are widely utilized to study combustion phenomena at engine-relevant conditions, and significant efforts are typically made to create a quiescent environment, particularly for investigations of autoignition chemistry. Opposed-piston configurations can be advantageous due to shorter compression times and reduced surface area to volume ratios. Each side must be actuated simultaneously, but this can be challenging in practice. These devices, like most RCMs, utilize hydraulics for actuation, speed control and arrestation of the piston at the end of the stroke; there is no mechanical control or linkage of the two piston trajectories. To quantify the magnitudes and effects of piston asynchronous behavior, this work employs both detailed experimental measurements and, for the first time, high-fidelity, Direct Numerical Simulation (DNS). The boundary conditions are carefully considered applying insight from high-resolution linear variable differential transformer (LVDT) measurements of the piston trajectory and a zero-dimensional kinematics model of the piston-shaft assembly. Sufficient resolution in the piston crevice region is used. The complicated fluid dynamical behavior that can evolve during piston compression and the ensuing delay processes due to offset timings from t offset = 0-10 ms is elucidated. It is found that near t offset = 6 ms and beyond, the boundary layer on the face of the first-seating piston can be sufficiently perturbed, due initially to reemergence of gas from the crevice of the firstseating piston, so that the adiabatic core can become degraded at long ignition delay times. Substantial mixing of colder gas into the interior of the reaction chamber can alter the measurements, similar to effects previously observed for improper piston crevice configuration. In conclusion, experimental techniques to mitigate asynchronous behavior are discussed and demonstrated.

33 ADVANCED PROPULSION SYSTEMS↗

DOE OSTI2024

Experimental Investigation of the Effect of Air-Handling and DME-Propane Blends on the Performance and Emissions of a 4-Cylinder CI Engine

Dimethyl ether (DME) is considered an excellent alternative to diesel because of its higher cetane number and lower carbon content. Additionally, DME can be blended with abundantly available propane with minimal modifications to the propane infrastructure. This paper focuses on an experimental investigation of the effect of air-handling i.e., boost pressure and exhaust gas recirculation (EGR), and DME-propane blends on the combustion and emissions performance of a light-duty, four-cylinder, compression ignition (CI) engine. Here, the boost pressure and EGR sweeps were carried out and showed that higher boost pressures resulted in increased brake thermal efficiencies (BTE) at the expense of higher NOx emissions which could be reduced by an increase in EGR. The fuel sweeps were carried out at 0, 15 and 25% propane (neat, 85% and 75% DME) with 0% and 25% EGR. The fuel sweeps indicated that the ignition delay (ID) increased and burn duration (BD) decreased monotonically when the blend increased to 25% propane/75% DME. The results suggest optimum engine performance with neat DME at 105 kPa boost pressure and 25% EGR with propane addition improving the BTE with negligible increase in emissions. Higher contents of Propane, up to 25%, did not affect the variability of combustion, with standard deviations of burn duration and peak cylinder pressures below 1% for all test cases.

air-handling↗

DOE OSTI2024

The role of stereochemistry in combustion processes

Stereochemical effects significantly influence chemical processes, yet it is not well understood if they are a leading source of uncertainty in combustion modeling. Stereochemistry influences a combustion model (i) at the earliest stage of its construction when mapping the reaction network, (ii) in the computation of individual thermochemical and rate parameters, and (iii) in the prediction of combustion observables. The present work reviews the importance of enumerating stereochemical species and reactions at each of these steps. Further, it analyzes the separate influence of several types of stereochemistry, including geometric, optical, and fleeting transition state diastereomers. Three reaction networks serve to examine which stages of low-temperature oxidation are most affected by stereochemistry, including the first and second oxidation of n-butane, the third oxidation of n-pentane, and the early stages of pyrolysis of 1- and 2-pentene. The 149 reactions in the n-butane mechanism are expanded to 183 reactions when accounting for diastereomerism. Each of these 183 reactions is parameterized with ab initio kinetics computations to determine that, for the n-butane mechanism, the median factor of diastereomeric deviation is 3.5 at 360 K for rate constants and as high as 1.6 for mechanism reactivity, in terms of ignition delay times, as opposed to a mechanism without stereochemical expansion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Experimental and modeling study of the autoignition behavior of a saturated heterocycle: Pyrrolidine

Experiments are conducted in both rapid compression machine (RCM) and shock tube (ST) to better quantify autoignition behavior (e.g., ignition delay, heat release) and understand heteroatomic effects in heterocyclic compounds, which are important reference components for the combustion of biomass-derived liquid fuels. These tests focus on the nitrogen-containing, five-membered saturated ring, pyrrolidine, at diluted conditions covering pressures of 20 and 50 bar, temperatures of 720–1450 K and a range of stoichiometries (ϕ = 0.5–2). A chemical kinetic model is developed and coupled to an existing combustion kinetics framework describing key nitrogen containing intermediates (e.g. pyrrole, ammonia and NOx). H-abstraction reactions by OH, H, CH 3 and HO 2 , are determined using ab-initio transition state theory methods, while analogies to cyclopentane are adopted for many other reactions, such as ring-opening. Here, the autoignition measurements reveal the lack of negative temperature coefficient (NTC) behavior and low-temperature chemistry for pyrrolidine, as opposed to its saturated hydrocarbon analogue, cyclopentane. Interestingly, at the lowest temperatures (T < 750 K), the reactivity of cyclopentane is greater than pyrrolidine, while at higher temperatures, pyrrolidine becomes more reactive. Agreement between the experimental measurements and the model is good, and it is found that H-abstraction reactions by HO 2 and ensuing chemistry play key roles in controlling the reactivity of this cyclic amine. Most of the fluxes, i.e., >70 %, are predicted to move through 1- or 2-pyrroline (C 4 H 7 N) and then the cyclic C 4 H 6 N radical, at both lower and higher temperatures, to form either CH 2 CHCHCHNH via ring-opening or pyrrole via β-scission. It appears that the ring opens more easily at lower temperature whereas the C–H β-scission dominates at higher temperature and lower pressure, such that the reaction of the fuel radical intermediate carrying an unpaired electron on the nitrogen atom with HO 2 is the next most notable in promoting oxidation. When comparing pyrrolidine and cyclopentane, which exhibits distinct pathways in different temperature regimes, the pyrrolidine pathways and sensitivity analysis align more closely to the high temperature case of cyclopentane where the important role of HO 2 radicals is seen to provide chain branching through HO 2 reaction with the fuel, accompanied by H 2 O 2 formation and decomposition to OH. The formation of 5-membered diene rings and ring opening reactions are also found to be highly relevant. Of particular note, it is found that there is little influence of small molecule nitrogen-chemistry, e.g., NH 2 , HCN, NO/NO 2 on the reactivity of the pyrrolidine mixtures investigated here where no recirculated combustion gases are included.

Autoignition↗