Experimental and modeling study of the thermal decomposition of methyl decanoate

The experimental study of the thermal decomposition of methyl decanoate was performed in a jet-stirred reactor at temperatures ranging from 773 to 1123 K, at residence times between 1 and 4 s, at a pressure of 800 Torr (106.6 kPa) and at high dilution in helium (fuel inlet mole fraction of 0.0218). Species leaving the reactor were analyzed by gas chromatography. Main reaction products were hydrogen, carbon oxides, small hydrocarbons from C₁ to C₃, large 1-olefins from 1-butene to 1-nonene, and unsaturated esters with one double bond at the end of the alkyl chain from methyl-2-propenoate to methyl-8-nonenoate. At the highest temperatures, the formation of polyunsaturated species was observed: 1,3-butadiene, 1,3-cyclopentadiene, benzene, toluene, indene, and naphthalene. These results were compared with previous ones about the pyrolysis of n-dodecane, an n-alkane of similar size. The reactivity of both molecules was found to be very close. The alkane produces more olefins while the ester yields unsaturated oxygenated compounds.A detailed kinetic model for the thermal decomposition of methyl decanoate has been generated using the version of software EXGAS which was updated to take into account the specific chemistry involved in the oxidation of methyl esters. This model contains 324 species and 3231 reactions. It provided a very good prediction of the experimental data obtained in jet-stirred reactor. The formation of the major products was analyzed. The kinetic analysis showed that the retro-ene reactions of intermediate unsaturated methyl esters are of importance in low reactivity systems.     

Experimental study of the oxidation of methyl oleate in a jet-stirred reactor

The experimental study of the oxidation of a blend containing n-decane and a large unsaturated ester, methyl oleate, was performed in a jet-stirred reactor over a wide range of temperature covering both low and high temperature regions (550-1100 K), at a residence time of 1.5 s, at quasi atmospheric pressure with high dilution in helium (n-decane and methyl oleate inlet mole fractions of 1.48 × 10⁻³ and 5.2 × 10⁻⁴) and under stoichiometric conditions.The formation of numerous reaction products was observed. At low and intermediate temperatures, the oxidation of the blend led to the formation of species containing oxygen atoms like cyclic ethers, aldehydes and ketones deriving from n-decane and methyl oleate. At higher temperature, these species were not formed anymore and the presence of unsaturated species was observed. Because of the presence of the double bond in the middle of the alkyl chain of methyl oleate, the formation of some specific products was observed. These species are dienes and esters with two double bonds produced from the decomposition paths of methyl oleate and some species obtained from the addition of H-atoms, OH and HO₂ radicals to the double bond.Experimental results were compared with former results of the oxidation of a blend of n-decane and methyl palmitate performed under similar conditions. This comparison allowed highlighting the similarities and the differences in the reactivity and in the distribution of the reaction products for the oxidation of large saturated and unsaturated esters.     

Experimental study of the oxidation of large surrogates for diesel and biodiesel fuels

The experimental study of the oxidation of two blend surrogates for diesel and biodiesel fuels, n-decane/n-hexadecane and n-decane/methyl palmitate (74/26 mol/mol), has been performed in a jet-stirred reactor over a wide range of temperatures covering both low, and high-temperature regions (550-1100 K), at a residence time of 1.5 s, at quasi atmospheric pressure with high dilution in helium (hydrocarbon inlet mole fraction of 0.002) and at stoichiometric conditions.Numerous reaction products have been identified and quantified. At low and intermediate temperatures (less than 1000 K), the formation of oxygenated species such as cyclic ethers, aldehydes and ketones has been observed for n-decane, n-hexadecane, and methyl palmitate. At higher temperature, the formation of these species was not observed any more, and small amounts of unsaturated species (olefins and unsaturated methyl esters) have been detected.Results obtained with methyl palmitate and n-hexadecane have been compared in order to highlight similarities and differences between large n-alkanes and methyl esters.     

Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran and co-workers for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet-stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO₂ production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.     

Experimental and chemical kinetic modeling study of small methyl esters oxidation: Methyl (E)-2-butenoate and methyl butanoate

This study examines the effect of unsaturation on the combustion of fatty acid methyl esters (FAME). New experimental results were obtained for the oxidation of methyl (E)-2-butenoate (MC, unsaturated C₄ FAME) and methyl butanoate (MB, saturated C₄ FAME) in a jet-stirred reactor (JSR) at atmospheric pressure under dilute conditions over the temperature range 850-1400 K, and two equivalence ratios (Φ=0.375,0.75) with a residence time of 0.07 s. The results consist of concentration profiles of the reactants, stable intermediates, and final products, measured by probe sampling followed by on-line and off-line gas chromatography analyses. The oxidation of MC and MB in the JSR and under counterflow diffusion flame conditions was modeled using a new detailed chemical kinetic reaction mechanism (301 species and 1516 reactions) derived from previous schemes proposed in the literature. The laminar counterflow flame and JSR (for ?=1.13) experimental results used were from a previous study on the comparison of the combustion of both compounds. Sensitivity analyses and reaction path analyses, based on rates of reaction, were used to interpret the results. The data and the model show that MC has reaction pathways analogous to that of MB under the present conditions. The model of MC oxidation provides a better understanding of the effect of the ester function on combustion, and the effect of unsaturation on the combustion of fatty acid methyl ester compounds typically found in biodiesel.     

An experimental and modeling study of the low- and high-temperature oxidation of cyclohexane

The experimental study of the oxidation of cyclohexane has been performed in a jet-stirred reactor at temperatures ranging from 500 to 1100 K (low- and intermediate temperature zones including the negative temperature-coefficient area), at a residence time of 2 s and for dilute mixtures with equivalence ratios of 0.5, 1, and 2. Experiments were carried out at quasi-atmospheric pressure (1.07 bar). The fuel and reaction product mole fractions were measured using online gas chromatography. A total of 34 reaction products have been detected and quantified in this study. Typical reaction products formed in the low-temperature oxidation of cyclohexane include cyclic ethers (1,2-epoxycyclohexane and 1,4-epoxycyclohexane), 5-hexenal (formed from the rapid decomposition of 1,3-epoxycyclohexane), cyclohexanone, and cyclohexene, as well as benzene and phenol. Cyclohexane displays high low-temperature reactivity with well-marked negative temperature-coefficient (NTC) behavior at equivalence ratios 0.5 and 1. The fuel-rich system (? = 2) is much less reactive in the same region and exhibits no NTC. To the best of our knowledge, this is the first jet-stirred reactor study to report NTC in cyclohexane oxidation. Laminar burning velocities were also measured by the heated burner method at initial gas temperatures of 298, 358, and 398 K and at 1 atm. The laminar burning velocity values peak at ? = 1.1 and are measured as 40 and 63.1 cm/s for T_i = 298 and 398 K, respectively. An updated detailed chemical kinetic model including low-temperature pathways was used to simulate the present (jet-stirred reactor and laminar burning velocity) and literature experimental (laminar burning velocity, rapid compression machine, and shock tube ignition delay times) data. Reasonable agreement is observed with most of the products observed in our reactor, as well as the literature experimental data considered in this paper.     

Catalytic partial oxidation of methyl acetate as a model to investigate the conversion of methyl esters to hydrogen

Rhodium and rhodium–ceria catalysts were investigated in the catalytic partial oxidation of methyl acetate, the simplest methyl ester, to better understand the conversion of biodiesel to hydrogen. Both catalysts were active in producing carbon monoxide, carbon dioxide, water, and hydrogen, although the rhodium–ceria catalyst demonstrates the higher conversion and the higher hydrogen selectivities at high gas hourly space velocity (GHSV). A low methyl acetate to oxygen feed ratio (C/O) favored the methyl acetate conversion, the hydrogen selectivity, and the carbon monoxide selectivity. Also, a high GHSV also improved the reactor performance. The experimental data show evidence that the oxidation of methyl acetate produces carbon monoxide and water as a primary step, instead of carbon dioxide and water. Overall, methyl acetate did not yield as much synthesis gas as biodiesel. The methyl ester functional group of biodiesel will limit the yield of hydrogen, so new catalysts targeting the decomposition of methyl esters to hydrogen should be investigated.     

An experimental and modeling study of methyl propanoate pyrolysis at low pressure

Methyl propanoate (MP) pyrolysis in a laminar flow reactor was studied at low pressure (30 Torr) within the temperature range from 1000 to 1500 K. About 30 products were detected and identified in the pyrolysis process using the photoionization mass spectrometry, including H₂, CO, CO₂, CH₃OH, CH₂O, CH₂CO, C1 to C4 hydrocarbons and radicals (such as CH₃, C₂H₅ and C₃H₃). Their mole fraction profiles versus temperature were also measured. For the unimolecular dissociation reactions, the rate constants were calculated by high precision theoretical calculations. Based on the theoretical calculations and measured mole fraction profiles of pyrolysis species, a kinetic model of MP pyrolysis containing 98 species and 493 reactions was developed. The model simulates the primary decomposition process well with the calculated rate constants. According to the rate of production analysis, the decomposition pathways of MP and the formation channels of both oxygenated and hydrocarbon products were discussed. It is concluded that the main decomposition pathway is MP → CH₂COOCH₃ → CH₃CO + CH₂O → CO.     

Detailed kinetic study of anisole pyrolysis and oxidation to understand tar formation during biomass combustion and gasification

Anisole was chosen as the simplest surrogate for primary tar from lignin pyrolysis to study the gas-phase chemistry of methoxyphenol conversion. Methoxyphenols are one of the main precursors of PAH and soot in biomass combustion and gasification. These reactions are of paramount importance for the atmospheric environment, to mitigate emissions from wood combustion, and for reducing tar formation during gasification. Anisole pyrolysis and stoichiometric oxidation were studied in a jet-stirred reactor (673–1173 K, residence time 2 s, 800 Torr (106.7 kPa), under dilute conditions) coupled with gas chromatography–flame ionization detector and mass spectrometry. Decomposition of anisole starts at 750 K and a conversion degree of 50% is obtained at about 850 K under both studied conditions. The main products of reaction vary with temperature and are phenol, methane, carbon monoxide, benzene, and hydrogen. A detailed kinetic model (303 species, 1922 reactions) based on a combustion model for light aromatic compounds has been extended to anisole. The model predicts the conversion of anisole and the formation of the main products well. The reaction flux analyses show that anisole decomposes mainly to phenoxy and methyl radicals in both pyrolysis and oxidation conditions. The decomposition of phenoxy radicals is the main source of cyclopentadienyl radicals, which are the main precursor of naphthalene and heavier PAH in these conditions.     

An experimental and modeling study of 2-methyl-1-butanol oxidation in a jet-stirred reactor

In an effort to understand the oxidation chemistry of new generation biofuels, oxidation of a pentanol isomer (2-methyl-1-butanol) was investigated experimentally in a jet-stirred reactor (JSR) at a pressure of 10 atm, equivalence ratios of 0.5, 1, 2 and 4 and in a temperature range of 700–1200 K. Concentration profiles of the stable species were measured using GC and FTIR. A detailed chemical kinetic mechanism including oxidation of various hydrocarbon and oxygenated fuels was extended to include the oxidation chemistry of 2-methyl-1-butanol, the resulting mechanism was used to simulate the present experiments. In addition to the present data, recent experimental data such as ignition delay times measured in a shock tube and laminar flame speeds were also simulated with this mechanism and satisfactory results were obtained. Reaction path and sensitivity analyses were performed in order to interpret the results.     

Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate

Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet-stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.     

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.     

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.     

Experimental and kinetic modeling study of 2-butanol pyrolysis and combustion

2-Butanol (sC₄H₉OH) pyrolysis has been studied in a flow reactor with the synchrotron vacuum ultraviolet photoionization mass spectrometry combined with the molecular-beam sampling technique. The pyrolysis species were identified and their mole fractions were determined. Four pressures of 5, 30, 150 and 760 Torr were selected to study the pressure dependence of 2-butanol pyrolysis chemistry. The temperature- and pressure-dependent rate constants of unimolecular reactions of 2-butanol were calculated with the RRKM/Master Equation method. With the help of theoretical calculations, a detailed kinetic model consisting of 160 species and 1038 reactions was developed to simulate the 2-butanol pyrolysis. It is concluded that the mole fractions of pyrolysis species are very sensitive to the 2-butanol unimolecular reaction rates. To enhance the accuracy, the model is further validated by the species profiles in shock tube pyrolysis, a rich laminar premixed flame, oxidation data from jet-stirred reactor, ignition delay times, and laminar flame speed. Good agreements between the predicted and measured results were obtained.     

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.     

Experimental and detailed kinetic model for the oxidation of a Gas to Liquid (GtL) jet fuel

The kinetics of oxidation, ignition, and combustion of Gas-to-Liquid (GtL) Fischer–Tropsch Synthetic kerosene as well as of a selected GtL-surrogate were studied. New experimental results were obtained using (i) a jet-stirred reactor – species profiles (10 bar, constant mean residence time of 1 s, temperature range 550–1150 K, equivalence ratios φ = 0.5, 1, and 2), (ii) a shock tube – ignition delay time (≈16 bar, temperature range 650–1400 K, φ = 0.5 and 1), and (iii) a burner – laminar burning velocity (atmospheric pressure, preheating temperature = 473 K, 1.0 ? φ ? 1.5). The concentrations of the reactants, stable intermediates, and final products were measured as a function of temperature in the jet-stirred reactor (JSR) using probe sampling followed by on-line Fourier Transformed Infra-Red spectrometry, and gas chromatography analyses (on-line and off-line). Ignition delay times behind reflected shock waves were determined by measuring time-dependent CH^* emission at 431 nm. Laminar flame speeds were obtained in a bunsen-type burner by applying the cone angle method. Comparison with the corresponding results for Jet A-1 showed comparable combustion properties. The GtL-fuel oxidation was modeled under these conditions using a detailed chemical kinetic reaction mechanism (8217 reactions vs. 2185 species) and a 3-component model fuel mixture composed of n-decane, iso-octane (2,2,4-trimethyl pentane), and n-propylcyclohexane. The model showed good agreement with concentration profiles obtained in a JSR at 10 bar. In the high temperature regime, the model represents well the ignition delay times for the fuel air mixtures investigated; however, the calculated delays are longer than the measurements. It was observed that the ignition behavior of the surrogate fuel is mainly influenced by n-alkanes and not by the addition of iso-alkanes and cyclo-alkanes. The simulated laminar burning velocities were found in excellent agreement with the measurements. No deviation between burning velocity data for the GtL-surrogate and GtL was seen, within the uncertainty range. The presented data on ignition delay times and burning velocities agree with earlier results obtained for petrol-derived jet fuel. The suitability of both the current detailed reaction model and the selected GtL surrogate was demonstrated. Finally, our results support the use of the GtL fuel as an alternative jet fuel.     

Premixed ignition behavior of C9 fatty acid esters: A motored engine study

An experimental study on the premixed ignition behavior of C₉ fatty acid esters has been conducted in a motored CFR engine. For each test fuel, the engine compression ratio was gradually increased from the lowest point (4.43) to the point where significant high temperature heat release (HTHR) was observed. The engine exhaust was sampled and analyzed through GC-FID/TCD and GC-MS. Combustion analysis showed that the four C₉ fatty acid esters tested in this study exhibited evidently different ignition behavior. The magnitude of low temperature heat release (LTHR) follows the order, ethyl nonanoate > methyl nonanoate ? methyl 2-nonenoate > methyl 3-nonenoate. The lower oxidation reactivity for the unsaturated fatty acid esters in the low temperature regime can be explained by the reduced amount of six- or seven-membered transition state rings formed during the oxidation of the unsaturated esters due to the presence of a double bond in the aliphatic chain of the esters. The inhibition effect of the double bond on the low temperature oxidation reactivity of fatty acid esters becomes more pronounced as the double bond moves toward the central position of the aliphatic chain. GC-MS analysis of exhaust condensate collected under the engine conditions where only LTHR occurred showed that the alkyl chain of the saturated fatty acid esters participated in typical paraffin-like low temperature oxidation sequences. In contrast, for unsaturated fatty acid esters, the autoignition can undergo olefin ignition pathways. For all test compounds, the ester functional group remains largely intact during the early stage of oxidation.     

Experimental and kinetic modeling study of i-butanol pyrolysis and combustion

i-Butanol (iC₄H₉OH) pyrolysis has been studied in a flow reactor with synchrotron vacuum ultraviolet photoionization mass spectrometry combined with molecular-beam sampling technique. The pyrolysis species were identified and their mole fractions were determined. Three pressures of 30, 150 and 760 Torr were selected to study the pressure effect of i-butanol chemistry. A detailed kinetic model consisting of 186 species and 1294 reactions was developed to simulate i-butanol high temperature chemistry. To enhance the accuracy, the model was further validated by the species profiles in shock tube pyrolysis, laminar premixed flames, oxidation data from jet-stirred reactor, ignition delay times, and flame speeds. Good agreement between the predicted and measured results was obtained.