Experimental and kinetic modeling study of methyl butanoate and methyl butanoate/methanol flames at different equivalence ratios and C/O ratios

Premixed laminar methyl butanoate/oxygen/argon and methyl butanoate/methanol/oxygen/argon flames were studied with tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam sampling mass spectrometry at 30 torr (4.0 kPa). Three flames were investigated in the experiment: MB (methyl butanoate) flame F1.54 (? = 1.54, C/O = 0.479), MB flame F1.67 (? = 1.67, C/O = 0.511) and MB/methanol flame F1.67M (? = 1.67, C/O = 0.479). By measuring the signal intensities at different distances from the burner surface, the mole fraction profiles of intermediates are derived. Experimental results show that the flame front shifts downstream and peak mole fractions of intermediates increase remarkably with the increase of equivalence ratio for pure MB fuel. When methanol is added, the peak mole fractions of most intermediates including those of soot precursors decrease remarkably at the same equivalence ratio, while peaks of soot precursors vary little (only slightly decreasing) at same C/O ratio. It is concluded that the formation of soot precursors is more sensitive to C/O ratio than to equivalence ratio. Besides, more CO₂ is produced near the burner surface in MB flame than that in MB/methanol flame, and this validates an early production of CO₂ in methyl ester oxidation. In addition, a modified MB detailed mechanism is used to model flame structure, and improved agreements between the experimental and predicted results are realized. Based on the simulation results, reaction flux and sensitivity are analyzed for CO₂ and C₃H₃, respectively.     

An experimental and kinetic modeling study of n-butanol combustion

n-Butanol is a fuel that has been proposed as an alternative to conventional gasoline and diesel fuels. In order to better understand the combustion characteristics of n-butanol, this study presents new experimental data for n-butanol in three experimental configurations. Species concentration profiles are presented in jet stirred reactor (JSR) at atmospheric conditions and a range of equivalence ratios. The laminar flame speed obtained in an n-butanol premixed laminar flame is also provided. In addition, species concentration profiles for n-butanol and n-butane in an opposed-flow diffusion flame are presented. The oxidation of n-butanol in the aforementioned experimental configurations has been modeled using an improved detailed chemical kinetic mechanism (878 reactions involving 118 species) derived from a previously proposed scheme in the literature. The proposed mechanism shows good qualitative agreement with the various experimental data. Sensitivity analyses and reaction path analyses have been conducted to interpret the results from the JSR and opposed-flow diffusion flame. It is shown that the main reaction pathway in both configurations is via H-atom abstraction from the fuel followed by β-scission of the resulting fuel radicals. Several unimolecular decomposition reactions are important as well. This study gives a better understanding of n-butanol combustion and the product species distribution.     

Studies of C4 and C10 methyl ester flames

The oxidation of three model biodiesel fuels, namely methyl butanoate (C₅H₁₀O₂, CAS No. 623-42-7), methyl crotonate (C₅H₈O₂, CAS No. 623-43-8), and methyl decanoate (C₁₁H₂₂O₂, CAS No. 110-42-9) was investigated in laminar premixed and non-premixed flames. The experiments were conducted in the counterflow configuration at atmospheric pressure, for a wide range of equivalence or inert-dilution ratios, and elevated reactant temperatures. Laminar flame speeds and local extinction strain rates were determined by measuring the flow velocities using digital particle image velocimetry. The experimental data were compared against those derived for flames of n-alkanes of similar carbon number, in order to assess the effects of saturation, the length of carbon chain, and the presence of the ester group. Several recent chemical kinetic models were tested against the experimental data, and major differences were identified and assessed. The accuracy of the Lennard–Jones potential parameters assigned to the methyl esters in the transport databases of the different models was evaluated and new values were estimated. Insight was provided into the high-temperature kinetic pathways of methyl esters in flame environments. Additionally, the reduced sooting propensity of methyl ester flames compared to n-alkane flames was investigated computationally.     

Autoignition of binary fuel blends of n-heptane and C7 esters in a motored engine

Autoignition of binary fuel blends of n-heptane and C₇ esters, i.e., n-heptane/methyl hexanoate blend and n-heptane/methyl 3-hexenoate blend, was studied in a modified CFR engine at an equivalence ratio of 0.25 and an intake temperature of 155 °C. Heat release analyses showed that the n-heptane/methyl hexanoate blend exhibits stronger cool flame response than the n-heptane/methyl 3-hexenoate blend within the test range of this study, suggesting that methyl 3-hexenoate is less reactive than methyl hexanoate at low temperatures due to the presence of a double bond in the aliphatic chain. Based on quantitative product analyses, major oxidation pathways of methyl 3-hexenoate and of methyl hexanoate were identified. Consistent with the existing literature, at low to intermediate temperatures, methyl hexanoate was observed to undergo paraffinic low temperature oxidation pathways with the ester functional group remaining largely intact, while methyl 3-hexenoate exhibits olefinic oxidation characteristics. Moreover, it was observed that a key feature in the oxidation of methyl 3-hexenoate is the attack of radical species to the double bond in its aliphatic chain, resulting in the formation of unsaturated esters, an epoxy ester, and an aldehyde.     

Experimental and kinetic modeling study of pyrolysis and oxidation of n-decane

The pyrolysis of n-decane was investigated in a flow reactor at 5, 30, 150 and 760 Torr, and the oxidation of n-decane at equivalence ratios of 0.7, 1.0 and 1.8 was studied in laminar premixed flames at 30 Torr. In both experiments, synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) was used to identify combustion species and measure their mole fraction profiles. A new detailed kinetic model of n-decane with 234 species and 1452 reactions was developed for applications in intermediate and high temperature regions, and was validated against the experimental results in the present work. The model was also validated against previous experimental data on n-decane combustion, including species profiles in pyrolysis and oxidation in high pressure shock tube and atmospheric pressure flow reactor, jet stirred reactor oxidation, atmospheric pressure laminar premixed flame, counterflow diffusion flame and global combustion parameters such as laminar flame speeds and ignition delay times. In general, the performance of the present model in reproducing these experimental data is reasonably good. Sensitivity analysis and rate of production analysis were conducted to understand the decomposition processes of n-decane.     

Experimental study of the autoignition of C8H16O2 ethyl and methyl esters in a motored engine

Autoignition of two biodiesel surrogates, methyl heptanoate and ethyl hexanoate, was studied in a motored CFR engine at an equivalence ratio of 0.25 and an intake temperature of 155 °C. The engine compression ratio was gradually increased from the lowest point (4.43) to the point where significant high temperature heat release (HTHR) occurred. Within the test range of this work, both of the two esters exhibited evident cool flame behavior. At the same compression ratio, methyl heptanoate was observed to have both an earlier onset and a higher magnitude of low temperature heat release (LTHR) than ethyl hexanoate, indicating that methyl heptanoate is more reactive in the low temperature region than ethyl hexanoate. GC–MS analyses of the reaction intermediates from the oxidation of the two esters showed that the alkyl chain of fatty acid esters experiences the typical paraffin-like low temperature oxidation sequence. Based on the observations from GC–MS analyses, major low temperature oxidation pathways of ethyl hexanoate are proposed in this work. Also, it is observed that the abstraction of H-atoms on the α-carbon of the ester carbonyl group plays an important role in the oxidation of fatty acid esters. In addition, the identification of hexanoic acid among the reaction intermediates from low temperature oxidation of ethyl hexanaoate together with the observation of more fuel carbon being converted to C₂H₄ during ethyl hexanoate oxidation than during methyl heptanoate oxidation provide evidence for the existence of the six-centered unimolecular elimination reaction during low temperature oxidation of ethyl esters.     

Experimental kinetic study of the oxidation of p-xylene in a JSR and comprehensive detailed chemical kinetic modeling

The oxidation of para-xylene was studied in a jet-stirred reactor at atmospheric pressure under dilute conditions. New experimental results were obtained over the high-temperature range 900-1300 K, and variable equivalence ratios (0.5?Φ?1.5). They consisted of concentration profiles of the reactants, stable intermediates, and final products, measured by sonic probe sampling followed by on-line GC-MS and off-line GC-TCD-FID and GC-MS analyses. The oxidation of para-xylene under these conditions was modeled using a detailed chemical kinetic reaction mechanism (160 species and 1175 reactions, most of them reversible) deriving from a previous scheme proposed for the ignition, oxidation, and combustion of simple aromatics (benzene, toluene, styrene, n-propylbenzene). The proposed kinetic scheme was also successfully tested against the ignition delays of p-xylene-oxygen-argon mixtures, and the combustion of p-xylene in a low-pressure methane-oxygen-nitrogen flame doped with p-xylene, confirming its validity. Sensitivity analyses and reaction path analyses, based on rates of reaction, were used to interpret the results.     

Evaluation and optimization of two stage sequential in situ transesterification process for fatty acid methyl ester quantification from microalgae

This study demonstrates a direct transesterification (DT) method for reliable quantification of microalgal lipid. Primary screening of various transesterification methods and the types of biomass (wet, oven dried and lyophilized) were performed with heterotrophically grown Chlorella sp. FC2 IITG which revealed two stage DT with lyophilized biomass using NaOH in first stage and H₂SO₄ in second stage as the best combination with fatty acid methyl ester (FAME) yield of 39.17% (w/w, dry cell weight). Further optimization of transesterification parameters for selected method using response surface methodology, predicted the optimum values for catalyst to biomass ratio 0.67 (w/w) and 2.07 (v/w), methanol to biomass ratio 49.51 (v/w) and 61.07 (v/w) and reaction time 19.33 (min) and 10 (min) for first and second stages respectively. The optimum conditions showed 462.6% and 445.4% increment in FAME yield when compared with Bligh and Dyer method for Chlorella sp. FC2 IITG and Chlorella sorokiniana FC6 IITG respectively with highest transesterification efficiency of 98.96%. Improved transesterification efficiency of two stage DT was attributed to efficient destabilization of cell wall as confirmed by scanning electron microscopic imaging. FAME produced via DT of Chlorella sp. FC2 IITG satisfied most of the biodiesel properties as per ASTM D6751 and hence, could be an alternative to petro-diesel.     

An experimental and kinetic modeling study of methyl formate low-pressure flames

The oxidation of methyl formate (CH₃OCHO), the simplest methyl ester, is studied in a series of burner-stabilized laminar flames at pressures of 22–30 Torr and equivalence ratios (Φ) from 1.0 to 1.8 for flame conditions of 25–35% fuel. Flame structures are determined by quantitative measurements of species mole fractions with flame-sampling molecular-beam synchrotron photoionization mass spectrometry (PIMS). Methyl formate is observed to be converted to methanol, formaldehyde and methane as major intermediate species of mechanistic relevance. Smaller amounts of ethylene and acetylene are also formed from methyl formate oxidation. Reactant, product and major intermediate species profiles are in good agreement with the computations of a recently developed kinetic model for methyl formate oxidation [S. Dooley, M.P. Burke, M. Chaos, Y. Stein, F.L. Dryer, V.P. Zhukov, O. Finch, J.M. Simmie, H.J. Curran, Int. J. Chem. Kinet. 42 (2010) 527–529] which shows that hydrogen abstraction reactions dominate fuel consumption under the tested flame conditions. Radical–radical reactions are shown to be significant in the formation of a number of small concentration intermediates, including the production of ethyl formate (C₂H₅OCHO), the subsequent decomposition of which is the major source of observed ethylene concentrations. The good agreement of model computations with this set of experimental data provides a further test of the predictive capabilities of the proposed mechanism of methyl formate oxidation. Other salient issues in the development of this model are discussed, including recent controversy regarding the methyl formate decomposition mechanism, and uncertainties in the experimental measurement and modeling of low-pressure flame-sampling experiments. Kinetic model computations show that worst-case disturbances to the measured temperature field, which may be caused by the insertion of the sampling cone into the flame, do not alter mechanistic conclusions provided by the kinetic model. However, such perturbations are shown to be responsible for disparities in species location between measurement and computation.     

Characteristics of flamelets in spray flames formed in a laminar counterflow

A two-dimensional numerical simulation of a spray flame formed in a laminar counterflow is presented, and the flamelet characteristics are studied in detail. The effects of strain rate, equivalence ratio, and droplet size are examined in terms of mixture fraction and scalar dissipation rate. n-Decane (C₁₀H₂₂) is used as a liquid spray fuel, and the droplet motion is calculated by the Lagrangian method without the parcel model. A one-step global reaction is employed for the combustion reaction model. The results show that there appear large differences in the trends of gaseous temperature and mass fractions of chemical species in the mixture fraction space between the spray flame and the gaseous diffusion flame. The gas temperature in the spray flame is much higher than that in the gaseous diffusion flame. This is due to the much lower scalar dissipation rate and the coexistence of premixed and diffusion-limited combustion in the spray flame. For the spray flames, gas temperature and mass fractions of chemical species are not unique functions of the mixture fraction scalar dissipation rate. This is because the production rate of the mixture fraction, namely evaporation rate of the droplets, in the upstream region is not in proportion to its transport-diffusion rate in the downstream region. The behavior shows marked differences as the strain rate decreases, the equivalence ratio increases, or the droplet size decreases.     

A lean methane premixed laminar flame doped with components of diesel fuel: I. n-Butylbenzene

To better understand the chemistry involved in the combustion of components of diesel fuel, the structure of a laminar lean premixed methane flame doped with n-butylbenzene has been investigated. The inlet gases contained 7.1% (molar) methane, 36.8% oxygen, and 0.96% n-butylbenzene corresponding to an equivalence ratio of 0.74 and a ratio C₁₀H₁₄/CH₄ of 13.5%. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as diluent, with a gas velocity at the burner of 49.2 cm/s at 333 K. Quantified species included the usual methane C₀-C₂ combustion products, but also 16 C₃-C₅ hydrocarbons, and 7 C₁-C₃ oxygenated compounds, as well as 20 aromatic products. A new mechanism for the oxidation of n-butylbenzene is proposed whose predictions are in satisfactory agreement with measured species profiles in flames and flow reactor experiments. The main reaction pathways of consumption of n-butylbenzene have been derived from flow rate analyses.     

Study of antioxidant effect on oxidation stability and emissions in a methyl ester of neem oil fuelled DI diesel engine

Biodiesel as an alternative diesel fuel prepared from vegetable oils or animal fats has attracted more and more attention because of its renewable and environmental-friendly nature. But biodiesel undergoes oxidation and degenerate more quickly than mineral diesel. Further several studies report NO_x emissions increases for biodiesel fuel compared with conventional diesel fuel. In this paper, the experimental investigation of the effect of antioxidant additive (Butylated hydroxytoluene) on oxidation stability and NO_x emissions in a methyl ester of neem oil fuelled direct injection diesel engine has been reported. The antioxidant additive is mixed in various proportions (100–400 ppm) with methyl ester of neem oil. The oxidation stability was tested in Rancimat apparatus and emissions, performance in a computerized 4-stroke water-cooled single cylinder diesel engine of 3.5 kW rated power. Results show that the antioxidant additive is effective in increasing the oxidation stability and in controlling the NO_x emissions of methyl ester of neem oil fuelled diesel engines.     

Combustion and pyrolysis of iso-butanol: Experimental and chemical kinetic modeling study

The first reaction mechanism for iso-butanol (372 species and 8723 reversible elementary reactions) pyrolysis and combustion that includes pressure dependent kinetics and proposes reaction pathways to soot precursors has been automatically generated using the open-source software package RMG. High-pressure reaction rate coefficients for important hydrogen abstraction reactions from iso-butanol by hydrogen, methyl and HO₂ were calculated using quantum chemistry at the CBS-QB3 level. The mechanism was validated with recently published iso-butanol combustion experiments as well as new pyrolysis speciation data under diluted and undiluted conditions from 900 to 1100 K at 1.72 atm representative of fuel rich combustion conditions. Sensitivity and rate of production analysis revealed that the overall good agreement for the pyrolysis species, and in particular for the soot precursors like benzene, toluene and 1,3-cyclopentadiene, depends strongly on pressure dependent reactions involving the resonantly stabilized iso-butenyl radical. Laminar flame speed, opposed flow diffusion flame speciation profiles, and autoignition are also well-captured by the model. The agreement with speciation profiles for the jet-stirred reactor could be improved, in particular for temperatures lower than 850 K. Flux and sensitivity analysis for iso-butanol consumption revealed that this is primarily caused by uncertainty in iso-butanol + OH, iso-butanol + HO₂ and the low temperature peroxy chemistry rates. Further theoretical and quantum chemical studies are needed in understanding these rates to completely predict the combustion behavior of iso-butanol using detailed chemistry.     

A lean methane premixed laminar flame doped with components of diesel fuel part III: Indane and comparison between n-butylbenzene, n-propylcyclohexane and indane

To better understand the chemistry of the combustion of components of diesel fuel, the structure of a laminar lean premixed methane flame doped with indane has been investigated. The inlet gases contained 7.1% (molar) of methane, 36.8% of oxygen and 0.9% of indane corresponding to an equivalence ratio of 0.67 and a ratio C₁₀H₁₄/CH₄ of 12.8%. The flame has been stabilized on a burner at a pressure of 6.7 kPa (50 Torr) using argon as diluent, with a gas velocity at the burner of 49.1 cm s⁻¹ at 333 K. Quantified species included the usual methane C₀-C₂ combustion products, but also 16 C₃-C₅ non-aromatic hydrocarbons, 6 C₁-C₃ non-aromatic oxygenated compounds, as well as 22 aromatic products, namely benzene, toluene, xylenes, phenylacetylene, ethylbenzene, styrene, propenylbenzene, allylbenzene, n-propylbenzene, methylstyrenes, ethyltoluenes, trimethylbenzenes, n-butylbenzene, dimethylethylbenzene, indene, methylindenes, methylindane, benzocyclobutene, naphthalene, phenol, benzaldehyde, and benzofuran. A new mechanism for the oxidation of indane was proposed whose predictions were in satisfactory agreement with measured species profiles in both flames and jet-stirred reactor experiments. The main reaction pathways of consumption of indane have been derived from flow rate analyses in the two types of reactors. A comparison of the effect of the addition of three components of diesel fuel, namely indane, n-butylbenzene and n-propylcyclohexane (parts I and II of this series of paper), on the structure of a laminar lean premixed methane flame is also presented.     

Fatty acid methyl ester production from wet microalgal biomass by lipase-catalyzed direct transesterification

The aim of this work was to optimize the production of fatty acid methyl ester (FAME, biodiesel) from wet Nannchloropsis gaditana microalgal biomass by direct enzymatic transesterification. This was done in order to avoid the high cost associated with the prior steps of drying and oil extraction. Saponifiable lipids (SLs) from microalgal biomass were transformed to FAME using the lipase Novozyme 435 (N435) from Candida antarctica as the catalyst, and finally the FAME were extracted with hexane. t-Butanol was used as the reaction medium so as to decrease lipase deactivation and increase mass transfer velocity. A FAME conversion of 99.5% was achieved using wet microalgal biomass homogenized at 140 MPa to enhance cell disruption, a N435:oil mass ratio of 0.32, methanol added in 3 stages to achieve a total of 4.6 cm³ g⁻¹ of oil and 7.1 cm³ g⁻¹ oil of added t-butanol, with a reaction time of 56 h. The FAME conversion decreased to 57% after catalyzing three reactions with the same lipase batch. This work shows the influence of the polar lipids contained in the microalgal biomass both on the reaction velocity and on lipase activity.     

A reaction mechanism for gasoline surrogate fuels for large polycyclic aromatic hydrocarbons

This work aims to develop a reaction mechanism for gasoline surrogate fuels (n-heptane, iso-octane and toluene) with an emphasis on the formation of large polycyclic aromatic hydrocarbons (PAHs). Starting from an existing base mechanism for gasoline surrogate fuels with the largest chemical species being pyrene (C₁₆H₁₀), this new mechanism is generated by adding PAH sub-mechanisms to account for the formation and growth of PAHs up to coronene (C₂₄H₁₂). The density functional theory (DFT) and the transition state theory (TST) have been adopted to evaluate the rate constants for several PAH reactions. The mechanism is validated in the premixed laminar flames of n-heptane, iso-octane, benzene and ethylene. The characteristics of PAH formation in the counterflow diffusion flames of iso-octane/toluene and n-heptane/toluene mixtures have also been tested for both the soot formation and soot formation/oxidation flame conditions. The predictions of the concentrations of large PAHs in the premixed flames having available experimental data are significantly improved with the new mechanism as compared to the base mechanism. The major pathways for the formation of large PAHs are identified. The test of the counterflow diffusion flames successfully predicts the PAH behavior exhibiting a synergistic effect observed experimentally for the mixture fuels, irrespective of the type of flame (soot formation flame or soot formation/oxidation flame). The reactions that lead to this synergistic effect in PAH formation are identified through the rate-of-production analysis.     

Laminar flame propagation of atmospheric iso-cetane/air and decalin/air mixtures

Laminar flame speeds of iso-cetane/air and decalin/air mixtures were measured in the counterflow configuration at atmospheric pressure and an elevated unburned mixture temperature of 443 K. Axial flow velocities were measured along the stagnation streamline using the digital particle image velocimetry. The laminar flame speeds were determined by determining the variation of a reference flame speed as a function of strain rate and computationally assisted non-linear extrapolations. The data are the first to be reported in the literature, and they were modeled using a recently developed kinetic model that includes 187 species and 6086 elementary reactions. In general, the computed results were found to be in close agreement with the data. In order to get insight into kinetic effects on flame propagation, detailed sensitivity and reaction path analyses were performed using the computed flame structures. The results revealed that at the same equivalence ratio, laminar flame speeds of iso-cetane/air mixtures are lower than those of n-hexadecane/air mixtures. Additionally, it was found that the laminar flame speeds of iso-cetane/air and decalin/air mixtures are sensitive largely to C₀–C₄ kinetic subset, and that the lower reactivity of iso-cetane compared to n-hexadecane could be attributed to the higher production of relatively stable intermediates.