Search Results

In transportation sector, higher engine thermal efficiency is currently required to solve the energy crisis and environmental problems. In spark ignition (SI) engine, lean-burn strategy is the promising approach to improve thermal efficiency and lower emissions. Olefins are the attractive component for gasoline additives, because they are more reactive and have advantage in lean limit extension. However, owing to lower research octane number (RON), it is expected to exhibit the drawback to reducing the anti-knock performance. The experiments were performed using a single-cylinder engine for 6 fuel types including gasoline blends which have difference in RON varying between 90.4 and 100.2. The results showed that adding olefin content to the premium gasoline provided unfavorable effect on auto-ignition as the auto-ignition happened at unburned gas temperature of 808 K which was 52 K lower at excess air of 2.0. Thus, it reduced anti-knock performance.

Gasoline engines have the trace-knock phenomena induced by the fast combustion which happens a few times during 100 cycles. And that constrains the thermal efficiency improvement due to limiting the ignition timing advance. So the authors have been dedicating a trace-knock simulation so that we could obtain any pieces of information associated with trace-knock characteristics. This simulation consists of a turbulent combustion model, a cycle-by-cycle variation model and a chemical calculation subprogram. In the combustion model, a combustion zone is considered in order to obtain proper turbulent combustion speed through wide range of engine speed. From a cycle-by-cycle variation analysis of an actual gasoline engine, some trace-knock features were detected, and they were involved in the cycle-by-cycle variation model. And a reduced elementary reaction model of gasoline PRF (primary reference fuel) was customized to the knocking prediction, and it was used in the chemical calculation.

n-Tridecane is a low boiling point component of gas oil, and has been used as a single-component fuel for diesel spray and combustion experiments. However, no reduced chemical kinetic mechanisms for n-tridecane have been presented for three-dimensional modeling. A detailed mechanism developed by KUCRS (Knowledge-basing Utilities for Complex Reaction Systems), contains 1493 chemical species and 3641 reactions. Reaction paths during ignition process for n-tridecane in air computed using the detailed mechanism, were analyzed with the equivalence ratio of 0.75 and the initial temperatures of 650 K, 850 K, and 1100 K, which are located in the cool-flame dominant, negative-temperature coefficient, and blue-flame dominant regions, respectively.

The ignition delay times of n-C7H16, i-C8H18, and a blend of them at different fuel, O2 and N2 concentrations were computed using a detailed chemical kinetic mechanism generated by KUCRS. For each fuel, the dependences of ignition delay time on fuel, O2 and third body concentrations and on the heat capacity of a mixture were distilled to establish a power law equation for ignition delay time. For n-C7H16, ignition delay time τhigh without low-temperature oxidation at a high initial temperature between 1000 K and 1200 K was expressed using the scaling exponents for fuel, O2 and third body concentrations and heat capacity of 0.54, 0.29, 0.08, and - 0.38, respectively. Low-temperature oxidation induction time τ1 at a low initial temperature between 600 K and 700 K was expressed using the scaling exponents for fuel, O2 and third body concentrations and heat capacity of 0.03, 0.18, 0.04, and - 0.17, respectively.

To execute the computational fluid dynamics coupling with fuel chemistry in internal combustion engines, simplified chemical kinetic models which capture the low-temperature oxidation kinetics would be required. A steady-state analysis was applied to see the complicated reaction mechanism of alkylperoxy radicals by assuming the steady state for hydroperoxyalkyl (QOOH) and hydroperoxyalkylperoxy (OOQOOH) radicals. This analysis clearly shows the systematic trend of the reaction rate for the chain-branching and non-branching process of alkylperoxy (ROO) radicals as a function of the chain length and the carbon class. These trends make it possible to classify alkylperoxy radicals by their chemical structures, and suggest a reduced low-temperature oxidation chemistry.

One of the authors has proposed to use the decay rate of EHRR, the effective heat release rate, d2Q/dθ2 as an index for the rapid local combustion [1]. In this study, EHRR profiles and the cylinder gas pressure oscillations of the low and high speed knock are analyzed by using this index. A delayed rapid local combustion, such as an autoignition with small burned mass fraction can be detected. In the cases of the low speed knock, it has been agreed that a rapid local combustion is an autoignition. Although whether the cylinder gas oscillation is provoked by an auto ignition in a certain cycle or not is an irregular phenomenon, the auto ignition takes place in almost all of the cycles in the knocking condition. Mixture mass fraction burned by an auto ignition is large. A small auto ignition may induce a secondary auto ignition, in many cases, mass burned by the secondary auto ignition is extremely large.

Compression ratio of newly developed gasoline engines has been increased in order to improve fuel efficiency. But in-cylinder pressure around top dead center (TDC) before spark ignition timing is higher than expectation, because the low temperature oxidization (LTO) generates some heat. The overview of introduced calculation method taking account of the LTO heat of unburned gas, how in-cylinder pressure is revised and some knowledge of knocking prediction using chemical kinetics are shown in this paper.

The ignition characteristics of each component of natural gas and the chemical kinetic factors determining those characteristics were investigated using detailed chemical kinetic calculations. Ethane (C2H6) showed a relatively short ignition delay time with high initial temperature; the heat release profile was slow in the early stage of the ignition process and rapid during the late stage. Furthermore, the ignition delay time of C2H6 showed very low dependence on O2 concentration. In the ignition process of C2H6, HO2 is generated effectively by several reaction paths, and H2O2 is generated from HO2 and accumulated with a higher concentration, which promotes the OH formation rate of H2O2 (+ M) = OH + OH (+ M). The ignition characteristics for C2H6 can be explained by H2O2 decomposition governing OH formation at any initial temperature.

A fuel design concept for an HCCI engine based on chemical kinetics to optimize the heat release profile and achieve robust ignition was proposed, and applied to the design of the optimal methane-based blend. Ignition process chemistry of each single-component of natural gas, methane, ethane, propane, n-butane and isobutane, was analyzed using detailed chemical kinetic computations. Ethane exhibits low ignitability, close to that of methane, when the initial temperature is below 800 K, but higher ignitability, close to those of propane, n-butane and isobutane, when the initial temperature is above 1100 K. Furthermore, ethane shows a higher heat release rate during the late stage of the ignition process. If the early stage of an ignition process takes place during the compression stroke, this kind of heat release profile is desirable in an HCCI engine to reduce cycle-to-cycle variation during the expansion stroke.

Some experimental data indicate that an HCCI process of a highly diluted mixture is characterized with a two-stage profile of heat release after the heat release by low-temperature oxidation, and with slow CO oxidation into CO₂ at a low temperature. In the present paper, these characteristics are discussed using a detailed chemical kinetic model of normal heptane, and based on an authors' idea that an ignition process can be divided into five phases. The H₂O₂ loop reactions mainly contribute to heat release in a low-temperature region of the TI (thermal ignition) preparation phase. However, H+O₂+M=HO₂+M becomes the main contributor to heat release in a high-temperature region of the TI preparation phase. H₂O₂ is accumulated during the LTO (low-temperature oxidation) and NTC (negative temperature oxidation) phases, and drives the H₂O₂ loop reactions to increase the temperature during the TI preparation phase.

Gasoline includes various kinds of chemical species. Thus, the reaction model of gasoline components that includes the low-temperature oxidation and ignition reaction is necessary to investigate the method to control the combustion process of the gasoline engine. In this study, a gasoline combustion reaction model including n-paraffin, iso-paraffin, olefin, naphthene, alcohol, ether, and aromatic compound was developed. KUCRS (Knowledge-basing Utilities for Complex Reaction Systems) [1] was modified to produce paraffin, olefin, naphthene, alcohol automatically. Also, the toluene reactions of gasoline surrogate model developed by Sakai et al. [2] including toluene, PRF (Primary Reference Fuel), ethanol, and ETBE (Ethyl-tert-butyl-ether) were modified. The universal rule of the reaction mechanisms and rate constants were clarified by using quantum chemical calculation.

Ignition process chemistry was analyzed using a detailed chemical kinetic model of n-heptane generated by KUCRS (Knowledge-basing Utilities for Complex Reaction Systems), wherein pressure-dependent rate constants of the O₂ addition to alkyl radicals and hydroperoxy alkyl radicals and the thermal decomposition of ketohydroperoxides have been introduced. Then, the effect of the initial pressure and the individual effects of the initial fuel, O₂ and N₂ molar concentrations on a relationship between the initial temperature and the ignition delay were discussed. When the initial temperature increases, the branch of C₇H₁₄OOH removal into the second O₂ addition and the decomposition into C₇H₁₄cyO and OH is more sensitive to the pressure and the O₂ concentration, and thus, the LTO preparation phase is more affected by the pressure and the O₂ concentration. The LTO phase terminates mainly by the OH removal by intermediate species.

A systematic chemical lumping method has been proposed, based on the detailed kinetic analysis of hydrocarbon fuel ignitions. The model constructed by using this method contains two reaction sets, RO2 and fragment reaction package. The ignition characteristics of each fuel can be reflected by only adjusting several rate parameters in RO2 reaction package. From the comparison with detailed model, it was confirmed that this simplified model well reproduces the results of detailed one without missing the kinetics of hydrocarbon ignitions. We concluded that this new lumping approach has the possibility to be applicable to every hydrocarbon fuels.

Methyl butanoate (MB) and methyl decanoate (MD) are surrogates for biodiesel fuels. According to computational results with their detailed reaction mechanisms, MB and MD indicate shorter ignition delays than long alkanes such as n-heptane and n-dodecane do at an initial temperature over 1000 K. The high ignitability of these methyl esters was computationally analyzed by means of contribution matrices proposed by some of the authors. Due to the high acidity of an α-H atom in a carbonyl compound, hydroperoxy radicals are generated out of the equilibrium between forward and backward reactions of O₂ addition to methyl ester radicals by the internal transfer of an α-H atom in the initial stage of an ignition process. Some of the hydroperoxy methyl ester radicals can generate OH to activate initial reactions. MB has an efficient CH₃O formation path via CH₃ generated by the β-scission of an MB radical which has a radical site on the α-C atom to the carbonyl group.

Hydrocarbon thermal ignition in internal combustion engines is controlled by the balance of heat release rate by chemical reactions and internal energy formation or removal rate by adiabatic compression or expansion. Heat release rate can be described by a simple “Universal Rule”, that the heat release rate during the thermal ignition preparation period is determined by H2O2 loop composed of four elementary reactions. This rule was validated by sensitivity analysis and response analysis to perturbation of intermediate species concentrations. The rule was applied to clarify several subjects with experimental backgrounds, such as ignition characteristics of higher octane number fuels, an old and well-known knocking model and the influence of H2 addition.