Experimental and modeling study of the high-temperature combustion chemistry of tetrahydrofurfuryl alcohol

Lignocellulosic tetrahydrofuranic (THF) biofuels have been identified as promising fuel candidates for spark-ignition (SI) engines. To support the potential use as transportation biofuels, fundamental studies of their combustion and emission behavior are highly important. In the present study, the high-temperature (HT) combustion chemistry of tetrahydrofurfuryl alcohol (THFA), a THF based biofuel, was investigated using a comprehensive experimental and numerical approach.Representative chemical species profiles in a stoichiometric premixed methane flame doped with ～20% (molar) THFA at 5.3 kPa were measured using online gas chromatography. The flame temperature was obtained by NO laser-induced fluorescence (LIF) thermometry. More than 40 chemical products were identified and quantified. Many of them such as ethylene, formaldehyde, acrolein, allyl alcohol, 2,3-dihydrofuran, 3,4-dihydropyran, 4-pentenal, and tetrahydrofuran-2-carbaldehyde are fuel-specific decomposition products formed in rather high concentrations. In the numerical part, as a complement to kinetic modeling, high-level theoretical calculations were performed to identify plausible reaction pathways that lead to the observed products. Furthermore, the rate coefficients of important reactions and the thermochemical properties of the related species were calculated. A detailed kinetic model for high-temperature combustion of THFA was developed, which reasonably predicts the experimental data. Subsequent rate analysis showed that THFA is mainly consumed by H-abstraction reactions yielding several fuel radicals that in turn undergo either β-scission reactions or intramolecular radical addition that effectively leads to ring enlargement. The importance of specific reaction channels generally correlates with bond dissociation energies. Along THFA reaction routes, the derived species with cis configuration were found to be thermodynamically more stable than their corresponding trans configuration, which differs from usual observations for hydrocarbons.     

Asymptotic analysis of quasi-steady n-heptane droplet combustion supported by cool-flame chemistry

A skeletal chemical-kinetic mechanism for n-heptane cool flames is simplified to the maximum extent possible by introduction of steady-state approximations for intermediaries, following procedures employed previously in addressing two-stage ignition. A pair of ordinary differential equations in mixture-fraction space is thereby obtained, describing the quasi-steady structures of the temperature and heptylketohydroperoxide fields. Application of activation-energy asymptotics for the partial-burning regime to this pair of equations is shown to provide convenient expressions for flame structures and the extinction condition associated with maximally reduced chemistry. With the mixture-fraction co-ordinate related to radius, these results are used to address droplet-combustion experiments that have been performed in the International Space Station. Droplet diameters at extinction are predicted as functions of the oxygen concentration in the atmosphere and are compared with experiment. While the results are encouraging concerning qualitative predictions of dependences of extinction diameters on atmospheric conditions, there are noticeable quantitative differences that point to deficiencies in the analysis, likely resulting from a number of oversimplifications. Further investigation is therefore recommended.     

The role of cool-flame chemistry in quasi-steady combustion and extinction of n-heptane droplets

Experiments on the combustion of large n-heptane droplets, performed by the National Aeronautics and Space Administration in the International Space Station, revealed a second stage of continued quasi-steady burning, supported by low-temperature chemistry, that follows radiative extinction of the first stage of burning, which is supported by normal hot-flame chemistry. The second stage of combustion experienced diffusive extinction, after which a large vapour cloud was observed to form around the droplet. In the present work, a 770-step reduced chemical-kinetic mechanism and a new 62-step skeletal chemical-kinetic mechanism, developed as an extension of an earlier 56-step mechanism, are employed to calculate the droplet burning rates, flame structures, and extinction diameters for this cool-flame regime. The calculations are performed for quasi-steady burning with the mixture fraction as the independent variable, which is then related to the physical variables of droplet combustion. The predictions with the new mechanism, which agree well with measured autoignition times, reveal that, in decreasing order of abundance, H₂O, CO, H₂O₂, CH₂O, and C₂H₄ are the principal reaction products during the low-temperature stage and that, during this stage, there is substantial leakage of n-heptane and O₂ through the flame, and very little production of CO₂ with no soot in the mechanism. The fuel leakage has been suggested to be the source of the observed vapour cloud that forms after flame extinction. While the new skeletal chemical-kinetic mechanism facilitates understanding of the chemical kinetics and predicts ignition times well, its predicted droplet diameters at extinction are appreciably larger than observed experimentally, but predictions with the 770-step reduced chemical-kinetic mechanism are in reasonably good agreement with experiment. The computations show how the key ketohydroperoxide compounds control the diffusion-flame structure and its extinction.     

DNS Of the ignition process of n-heptane/air premixed combustion with low-temperature chemistry in turbulent boundary layer

In the present work, three-dimensional direct numerical simulation (DNS) of $n$-heptane/air premixed combustion in turbulent boundary layer was performed to explore the near-wall ignition process with low-temperature chemistry. A reduced chemical mechanism with 58 species and 387 elementary reactions for $n$-heptane combustion was used in the DNS. The general characteristics of the ignition process near the wall were examined. It was found that low-temperature ignition (LTI) dominates the upstream region, and high-temperature ignition (HTI) appears in the downstream region. The ignition process and the low-temperature chemistry pathways of the DNS are compared with those of a corresponding laminar case. It was found that the ignition process was affected by turbulence, which results in thickened reaction zones. However, the carbon flow analysis of low-temperature chemistry showed that turbulence rarely affects the low-temperature chemistry pathway. The combustion modes of various regions were scrutinized based on the budget terms of species transport equations and the chemical explosion mode analysis (CEMA). It was shown that the reaction term of ${\text{RO}}_2$ is significant during the LTI process of the upstream region, and the reaction terms of ${\text{CH}}_2\mathrm{O}$ and ${\text{CO}}_2$ are evident in the downstream region, indicating the occurrence of HTI. It was also shown that auto-ignition is dominant in the upstream region. With increasing streamwise distance, the contribution of flame propagation increases, which takes over that of auto-ignition in the near-wall region.     

正庚烷燃烧反应中间自由基的光谱测量

采用ICCD瞬态光谱探测系统和化学激波管,在点火温度1 408K,点火压力2.0atm,燃料摩尔分数1.0%,当量比1.0的条件下,拍摄了正庚烷燃烧过程中不同时刻的瞬态发射光谱,光谱曝光时间6μs,拍谱范围200～850nm。确认了在所拍光谱范围内主要是OH,CH和C2自由基的特征辐射光谱,表明小自由基OH,CH和C2是正庚烷燃烧过程中重要的反应中间产物。所拍时间分辨光谱显示,在正庚烷燃烧反应中,OH,CH和C2自由基一出现很快就达到其浓度峰值,但CH和C2自由基随着反应的进行迅速减少至消失,OH自由基持续的时间却长很多。实验结果为了解正庚烷燃烧反应微观过程和验证其燃烧反应机理提供了实验依据。     

Impact of nitric oxide on n-heptane and n-dodecane autoignition in a new high-pressure and high-temperature chamber

A New One Shot Engine (NOSE) was designed to simulate the thermodynamic conditions at High Pressure-High Temperature like an actual common-rail diesel engine in order to study the compression ignition of spray. The volume of the combustion chamber provided with large optical windows simplified the implementation of various optical diagnostics. The advantage of this kind of set-up in comparison to pre-burn or flue chambers is that the initial gas mixture can be well controlled in terms of species and mole fraction. The purpose of this work was to investigate the impact of nitric oxide (NO) on ignition delay (ID) for two fuels with different cetane numbers: n-heptane, and n-dodecane. In the thermodynamic conditions chosen (60?bar and over 800–900?K), NO had a strong effect on ID, with increases in NO tending to reduce the ignition delay. Results showed that ID and Lift-Off Length (LOL) presented the same trend as a function of temperature and NO concentration. Experimentally, at 900?K the ignition of n-dodecane was promoted by NO up to 100?ppm, whilst higher NO levels did not further promote ignition and a stabilization of the value has been noticed. For n-heptane, stronger promoting effects were observed in the same temperature conditions: the ignition delays were monotonically reduced with up to 200?ppm NO addition. At a lower temperature (800?K) the inhibiting effect was observed for n-dodecane for [NO] greater than 40?ppm, whereas only a promoting effect was observed for n-heptane. The experimental results of LOL showed that NO shortened LOL in almost all cases, and this varied with both the NO concentration and the mixture temperature. Thus, fuels with shorter ignition delays produce shorter lift-off lengths.     

Electromechanical properties and defect chemistry of high-temperature piezoelectric materials

Langasite and gallium phosphate are shown to exhibit piezoelectrically stimulated bulk acoustic waves up to at least 1,400 and 900 °C, respectively. Most critical issues are stoichiometry changes due to, e.g. low oxygen partial pressures, and high losses. Therefore, the paper discusses the atomistic transport and defect chemistry of those crystals and correlates them with the electromechanical properties. First, the defect chemistry of langasite is investigated. As long as the atmosphere is nearly hydrogen-free, the transport of charge carriers is governed by oxygen movement. A dominant role of hydrogen is observed in hydrogenous atmospheres. Based on the developed defect model, donors are expected to suppress the oxygen vacancy concentration and, thereby, the loss in langasite. The prediction is proven by niobium doping and found to be valid. A one-dimensional physical model of thickness shear mode resonators is summarized. The analysis of the resonance spectra showed that the loss of the resonators can be described satisfactorily by mechanical and electrical contributions expressed as effective viscosity and bulk conductivity, respectively. The mechanical loss in langasite is significantly impacted by the electrical conductivity due to the piezoelectric coupling. The effect of the piezoelectric coupling on the loss is negligible for gallium phosphate since it shows an extremely low electrical conductivity.     

Flame structure and combustion chemistry of energetic materials

A review of experimental studies of the structure of the flame of a number of energetic materials (EMs), such as ammonium perchlorate, ammonium dinitramide, RDX, HMX, and some model composite propellants on their bases, is presented. Experimental techniques for studying the flame structure of EMs, probe mass spectrometry and the thermocouple method, are described. An analysis of experimental data on the flame structure and combustion chemistry and a comparison of them with simulations within the framework of modern mechanisms of chemical reactions in EM flames are performed.     

A combustion chemistry study of tetramethylethylene in a laminar premixed low-pressure hydrogen flame

The combustion chemistry of tetramethylethylene (TME) was studied in a premixed laminar low-pressure hydrogen flame by combined photoionization molecular-beam mass spectrometry (PI-MBMS) and photoelectron photoion coincidence (PEPICO) spectroscopy at the Swiss Light Source (SLS) of the Paul Scherrer Institute in Villigen, Switzerland. This hexene isomer with the chemical formula C₆H₁₂ has a special structure with only allylic CH bonds. Several combustion intermediate species were identified by their photoionization and threshold photoelectron spectra, respectively. The experimental mole fraction profiles were compared to modeling results from a recently published kinetic reaction mechanism that includes a TME sub-mechanism to describe the TME/H₂ flame structure. The first stable intermediate species formed early in the flame front during the combustion of TME are 2-methyl-2-butene (C₅H₁₀) at a mass-to-charge ratio (m/z) of 70, 2,3-dimethylbutane (C₆H₁₄) at m/z 86, and 3-methyl-1,2-butadiene (C₅H₈) at m/z 68. Isobutene (C₄H₈) is also a dominant intermediate in the combustion of TME and results from consumption of 2-methyl-2-butene. In addition to these hydrocarbons, some oxygenated species are formed due to low-temperature combustion chemistry in the consumption pathway of TME under the investigated flame conditions.     

Multidimensional chemistry coordinate mapping approach for combustion modelling with finite-rate chemistry

A multidimensional chemistry coordinate mapping (CCM) approach is presented for efficient integration of chemical kinetics in numerical simulations of turbulent reactive flows. In CCM the flow transport is integrated in the computational cells in physical space, whereas the integration chemical reactions are carried out in a phase space made up of a few principal variables. Each cell in the phase space corresponds to several computational cells in the physical space, resulting in a speedup of the numerical integration. In reactive flows with small hydrocarbon fuels two principal variables have been shown to be satisfactory to construct the phase space. The two principal variables are the temperature (T) and the specific element mass ratio of the H atom (J _H). A third principal variable, σ=?J _H·?J _H, which is related to the dissipation rate of J _H, is required to construct the phase space for combustion processes with an initially non-premixed mixture. For complex higher hydrocarbon fuels, e.g. n-heptane, care has to be taken in selecting the phase space in order to model the low-temperature chemistry and ignition process. In this article, a multidimensional CCM algorithm is described for a systematic selection of the principal variables. The method is evaluated by simulating a laminar partially remixed pre-vaporised n-heptane jet ignition process. The CCM approach is then extended to simulate n-heptane spray combustion by coupling the CCM and Reynolds averaged Navier–Stokes (RANS) code. It is shown that the computational time for the integration of chemical reactions can be reduced to only 3–7%, while the result from the CCM method is identical to that of direct integration of the chemistry in the computational cells.     

Dual timestepping methods for detailed combustion chemistry

In this work, we develop and study several dual time integration methods for the solution of stiff, explosive differential equations governing combustion chemistry. Dual time integration is an implicit method wherein the sub-iteration process of each timestep is performed as a steady-state integration process, rather than the commonly used Newton–Raphson method. This allows stabilisation when nonlinear ignition events are contained within a timestep, providing considerable freedom in the choice of resolved phenomena. Timesteps may be chosen so as to resolve relatively long process timescales accurately rather than fast chemical timescales, something not possible with the common Newton's method. We illustrate this method using several backward difference formula methods and demonstrate the efficacy of our method in resolving low-frequency solutions of continuous flow stirred-tank reactors with periodic ignition–extinction events. We are able to step over ignition–extinction events with our stable, adaptive dual time method, and we study numerical convergence and error scaling on process timescales.     

Solving the riddle of the high-temperature chemistry of 1,3-dioxolane

This paper describes the improvement of the high-temperature chemistry of the 1,3-dioxolane model. New experiments, measured in a shock tube at the chair of High Pressure Gas Dynamics, are shown for 20 and 40 bar for ϕ = 0.5 and 2.0 with a dilution of 6 and 27, respectively, and also for in-air-like stoichiometric conditions. An already existing mechanism for 1,3-dioxolane is not able to reproduce these new experiments, therefore raising the need for improvements. The old model was mainly based on analogies, which are now replaced by quantum chemical calculations and new reaction pathways are included, revealing the rather unique combustion behavior of 1,3-dioxolane. Among these changes are ab-initio rate parameters for the H-atom abstraction reactions, the ring-opening reactions and the subsequent decomposition of the produced linear intermediates and a new important unimolecular reaction. Furthermore, the low-temperature chemistry of linear intermediates of 1,3-dioxolane was added to the mechanism, which turned out to be of critical importance even at high temperatures. To highlight the effect of each modification to the mechanism the new results from the quantum mechanical calculations and the additionally considered pathways are included and discussed in a step-wise manner. In the end, a new mechanism is presented that is able to reproduce all currently available shock tube experiments.     

Evaporation of two liquid droplets moving sequentially through high-temperature combustion products

We have performed an experimental study of the evaporation intensity for droplets in atomized-liquid flow moving through a flame of fixed height. Integral characteristics of the atomized-liquid evaporation process were evaluated. Evaporation of two water droplets moving sequentially one after the other through high-temperature combustion products is analyzed. A comparison of obtained data with available theoretical predictions is given.     

Optical diagnostics of diesel spray injections and combustion in a high-pressure high-temperature cell

We report on spatially and temporally resolved optical diagnostic measurements of propagation and combustion of diesel sprays introduced through a single-hole fuel injector into a constant volume, high-temperature, high-pressure cell. From shadowgraphy images in non-reacting environments of pure nitrogen, penetration lengths and dispersion angles were determined for non-vaporizing and vaporizing conditions, and found to be in reasonable agreement with standard models for liquid jet propagation and break-up.Quasi-simultaneous two-dimensional images were obtained of laser elastic light scattering, shadowgraphs and spectrally integrated flame emission in a reacting environment (cell temperature 850 K). In addition laser-induced incandescence was employed for the identification of soot-loaded regions. The simultaneously recorded spray images exhibit remarkable structural similarity and provide complementary information about the spray propagation and combustion process. The measurements also reveal the fuel vapor cloud extending well beyond the liquid core and close to the nozzle tip. Ignition takes place close to the tip of the spray within the mixing layer of fuel vapor and surrounding air. Soot is formed in the vapor core region at the tip of the liquid fuel jet. Our results support recently developed phenomenological model on diesel spray combustion.     

Premixed turbulent combustion modeling using tabulated detailed chemistry and PDF

Tabulated chemistry and presumed probability density function (PDF) approaches are combined to perform RANS modeling of premixed turbulent combustion. The chemistry is tabulated from premixed flamelets with three independent parameters: the equivalence ratio of the mixture, the progress of reaction, and the specific enthalpy, to account for heat losses at walls. Mean quantities are estimated from presumed PDFs. This approach is used to numerically predict a turbulent premixed flame diluted by hot burnt products at an equivalence ratio that differs from the main stream of reactants. The investigated flame, subjected to high velocity fluctuations, has a thickened-wrinkled structure. A recently proposed closure for scalar dissipation rate that includes an estimation of the coupling between flame wrinkling and micromixing is retained. Comparisons of simulations with experimental measurements of mean velocity, temperature, and reactants are performed.     

Large Eddy Simulation of MILD combustion using finite rate chemistry: Effect of combustion sub-grid closure

In this work, we present a detailed comparison between the conventional Partially Stirred Reactor (PaSR) combustion model and two implicit combustion models, named Quasi Laminar Finite Rate (QLFR) model and Laminar Finite Rate (LFR) model, respectively. Large Eddy Simulation (LES) is employed and the Adelaide Jet in Hot Co-flow (AJHC) burner is chosen as validation case. In the implicit combustion models, the filtered source term comes directly from the chemical term, without inclusion of turbulence effects. Results demonstrate that the two implicit models behave similarly to the conventional PaSR model, for the mean and root-mean-square of the temperature and species mass fractions, and that all models provide very satisfactory predictions, especially for the mean values. This justifies the use of implicit combustion models in low Damköhler number (Da ?≤? 1.0) systems. The QLFR model allows to reduce the computational cost of about three times, compared to the LFR model. Moreover, the comparison between two 4-step global mechanisms and the KEE58 mechanism proves the importance of finite rate chemistry in MILD combustion.     

Computationally efficient implementation of combustion chemistry in parallel PDF calculations

In parallel calculations of combustion processes with realistic chemistry, the serial in situ adaptive tabulation (ISAT) algorithm [S.B. Pope, Computationally efficient implementation of combustion chemistry using in situ adaptive tabulation, Combustion Theory and Modelling, 1 (1997) 41–63; L. Lu, S.B. Pope, An improved algorithm for in situ   adaptive tabulation, Journal of Computational Physics 228 (2009) 361–386] substantially speeds up the chemistry calculations on each processor. To improve the parallel efficiency of large ensembles of such calculations in parallel computations, in this work, the ISAT algorithm is extended to the multi-processor environment, with the aim of minimizing the wall clock time required for the whole ensemble. Parallel ISAT strategies are developed by combining the existing serial ISAT algorithm with different distribution strategies, namely purely local processing (PLP), uniformly random distribution (URAN), and preferential distribution (PREF). The distribution strategies enable the queued load redistribution of chemistry calculations among processors using message passing. They are implemented in the software x2f_mpi$x2f\_\mathit{mpi}$, which is a Fortran 95 library for facilitating many parallel evaluations of a general vector function. The relative performance of the parallel ISAT strategies is investigated in different computational regimes via the PDF calculations of multiple partially stirred reactors burning methane/air mixtures. The results show that the performance of ISAT with a fixed distribution strategy strongly depends on certain computational regimes, based on how much memory is available and how much overlap exists between tabulated information on different processors. No one fixed strategy consistently achieves good performance in all the regimes. Therefore, an adaptive distribution strategy, which blends PLP, URAN and PREF, is devised and implemented. It yields consistently good performance in all regimes. In the adaptive parallel ISAT strategy, the type and extent of redistribution is determined “on the fly” based on the prediction of future simulation time. Compared to the PLP/ISAT strategy where chemistry calculations are essentially serial, a speed-up factor of up to 30 is achieved. The study also demonstrates that the adaptive strategy has acceptable parallel scalability.