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.     

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.     

Experimental investigation on the conversion of fuel-N to NOx of quasi-particle in flue gas recirculation sintering process

Flue gas recirculation sintering process is a potential technology to decrease fuel consumption and NOx emissions compared with conventional sintering process. In present work, a vertical quartz tube reactor was used to investigate the combustion characteristics and conversion of fuel-N to NOx of quasi-particle. The mass conversion rate of quasi-particle increases with higher temperature. It was found that D₁ model is more appropriate than other models to describe quasi-particle combustion process through comparing correlation coefficients calculated by different mechanism models. Effects of temperature, coke size and proportion, circulating flue gas components on the conversion of fuel-N to NOx of quasi-particle were studied. The conversion rate of fuel-N to NOx of quasi-particle increases with higher temperature. With increasing coke size and proportion, the conversion rate of fuel-N to NOx decreases obviously. O₂ has a positive impact on the conversion of fuel-N to NOx of quasi-particle. CO could decrease the conversion rate of fuel-N to NOx by reducing NO directly or reacting with char to decrease NOx indirectly. CO₂ has an obviously inhibitory effect on the conversion of fuel-N to NOx of quasi-particle because it reacts with char to generate CO. The results were conducive to further understanding the combustion behavior and NOx formation mechanism of quasi-particle during flue gas recirculation sintering.     

A comprehensive experimental and modeling study of iso-pentanol combustion

Biofuels are considered as potentially attractive alternative fuels that can reduce greenhouse gas and pollutant emissions. iso-Pentanol is one of several next-generation biofuels that can be used as an alternative fuel in combustion engines. In the present study, new experimental data for iso-pentanol in shock tube, rapid compression machine, jet stirred reactor, and counterflow diffusion flame are presented. Shock tube ignition delay times were measured for iso-pentanol/air mixtures at three equivalence ratios, temperatures ranging from 819 to 1252 K, and at nominal pressures near 40 and 60 bar. Jet stirred reactor experiments are reported at 5 atm and five equivalence ratios. Rapid compression machine ignition delay data was obtained near 40 bar, for three equivalence ratios, and temperatures below 800 K. Laminar flame speed data and non-premixed extinction strain rates were obtained using the counterflow configuration. A detailed chemical kinetic model for iso-pentanol oxidation was developed including high- and low-temperature chemistry for a better understanding of the combustion characteristics of higher alcohols. First, bond dissociation energies were calculated using ab initio methods, and the proposed rate constants were based on a previously presented model for butanol isomers and n-pentanol. The model was validated against new and existing experimental data at pressures of 1–60 atm, temperatures of 650–1500 K, equivalence ratios of 0.25–4.0, and covering both premixed and non-premixed environments. The method of direct relation graph (DRG) with expert knowledge (DRGX) was employed to eliminate unimportant species and reactions in the detailed mechanism, and the resulting skeletal mechanism was used to predict non-premixed flames. In addition, reaction path and temperature A-factor sensitivity analyses were conducted for identifying key reactions at various combustion conditions.     

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.     

Impact of nitrogen oxides (NO,NO2, N2O) on the formation of soot

The emission of both nitrogen oxides and soot from combustion processes is still a matter of concern. When a flue gas recirculation (FGR) technique is applied, the presence of a given nitrogen oxide in the recirculated mixture can affect the emissions of other pollutants, such as soot, and be used for its control in a combustion process. In this context, the present work is focused on the identification of the effect of the main nitrogen oxides (NO, NO₂ and N₂O) present in combustion systems on soot and main product gases formation from the pyrolysis of ethylene, at atmospheric pressure and in the 975–1475 K temperature range. The experimental results are examined to assess the effectiveness of each nitrogen oxide in suppressing or boosting soot formation, to achieve the possible nitrogen oxides reduction, and to identify the elementary steps involved in the nitrogen oxides and ethylene conversion as function of the different nitrogen oxides. This analysis is supported on model calculations.     

废气再循环对二甲醚/甲醇均质压燃燃烧过程影响的试验研究

在单缸柴油机上进行了冷却废气再循环(EGR)对二甲醚(DME)/甲醇均质压燃(HCCI)燃烧过程影响的试验研究。结果表明,EGR对拓宽二甲醚/甲醇HCCI发动机的最大负荷作用不大;随着EGR率增大,主燃烧开始时刻和放热峰值明显后移,主燃烧持续期延长,放热峰值降低。EGR率为25%时的最大爆发压力比没有EGR时降低了近1.3 MPa,最大爆发压力出现的位置推迟了7°CA;EGR率增大,二甲醚/甲醇HCCI发动机的指示热效率升高。对应给定的EGR率,存在一个热效率较高的DME比例区间;HC和CO排放随EGR率的增大而增加,随DME比例的增加而降低,NOx排放接近于零。控制EGR率和DME比例是控制二甲醚/甲醇HCCI发动机燃烧过程、性能和排放的关键。     

An experimental and modeling study of propene oxidation. Part 1: Speciation measurements in jet-stirred and flow reactors

Propene is a significant component of Liquefied Petroleum Gas (LPG) and an intermediate in the combustion of higher order hydrocarbons. To better understand the combustion characteristics of propene, this study and its companion paper present new experimental data from jet-stirred (JSR) and flow reactors (Part I) and ignition delay time and flame speed experiments (Part II).     

Experimental and kinetic modeling study of 2,5-dimethylfuran pyrolysis at various pressures

The pyrolysis of 2,5-dimethylfuran (DMF) in a flow reactor was investigated at various pressures (30, 150 and 760 Torr) by synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). Dozens of pyrolysis products, especially a series of radicals and aromatics, were identified from the measurement of photoionization efficiency spectra; and their mole fraction profiles were measured at 780–1470 K. Phenol, 1,3-cyclopentadiene, 2-methylfuran, vinylacetylene and 1,3-butadiene were observed with high concentrations in the decomposition of DMF. The pressure-dependent rate constants of the major unimolecular decomposition reactions of DMF were theoretically calculated, and was adopted in the pyrolysis model of DMF with 285 species and 1173 reactions developed in the present work. The model was validated against the species profiles measured in both the present work and the previous pyrolysis studies of DMF. Based on the rate of production and sensitivity analyses, main pathways in the decomposition of DMF and the growth of aromatics were determined. The unimolecular decomposition to produce CH₃CHCCH and acetyl radicals, H-atom abstraction to produce 5-methyl-2-furanylmethyl radical, ipso substitution by H-atom to produce 2-methylfuran and H-atom attack to produce 1,3-butadiene and acetyl radical were concluded to dominate the primary decomposition of DMF. Further decomposition of 5-methyl-2-furanylmethyl radical leads to great production of phenol and 1,3-cyclopentadiene which can be readily converted to precursors of large aromatics such as cyclopentadienyl radical, phenyl radical and benzene. As a result, the formation of aromatics in the pyrolysis of DMF is promoted compared with the pyrolysis of cyclohexane and methylcyclohexane under very close conditions. This observation implies the potentially high sooting tendency of DMF, and emphasizes the necessity to investigate the sooting behavior and soot formation mechanism in DMF combustion for the potential application of DMF as an alternative engine fuel.     

The enigmatic mechanism of the flame ionization detector: Its overlooked implications for fossil fuel combustion modeling

The flame ionization detector (FID) has been a commercial analyzer now for about 50 years. It still finds significant use as a sensitive quantitative monitor of organic compounds in gas chromatography and for monitoring mixtures of hydrocarbons. Its carbon counting ability to integrate, for example, total unburned hydrocarbon emissions from a source, now is accepted without question. This is especially noteworthy as the fundamental chemistry on which the instrument is based has always been uncertain. Although now largely overlooked, its mechanism has significant implications and suggests that there is an underlying simplicity to hydrocarbon combustion. As a result, in the light of recent discoveries concerning the very rapid formation of a pool of hydrocarbon radicals in hydrocarbon combustion, a re-examination of the chemi-ionization mechanisms in hydrocarbon flames has been undertaken. Many of the previous speculations have been scrutinized and it is confirmed that the primary chemi-ionizing reaction of CH(X²Π) with O atoms is most likely the sole source in combustion including the FID. The oft suggested roles of electronically excited states of CH now are ruled out but with some slight uncertainty remaining on the still unknown importance of the metastable CH(a⁴Σ⁻) state in flames. The reason for the “equal per carbon” response of the FID with any hydrocarbon finally has been resolved. From isotopically labeled studies and measurements of the concentrations of CH and C₂ it is seen, under the same conditions, that different hydrocarbons do produce approximately the same levels of CH on a unit carbon basis. This results from the very rapid destruction and reformulation kinetics in the reaction zone of flames, and formation of a hydrocarbon radical pool that constitutes the unburned carbon. These radicals then are gradually eroded by the continuing oxidation or by soot precursor growth. As a result, the nature of the carbon in a hydrocarbon fuel is mainly irrelevant, only its quantity. The one well-documented exception has always been C₂H₂ but the data now show this so-called anomalous behavior to be no more than a reflection of its uniquely slower combustion nature in the reaction zone. It is not apparent in substituted acetylene fuels. Close to the reaction zone its kinetics produce a larger profile of unburned carbon that is evidenced by enhanced levels observed for CH and C₂. The nature of the specific responses of the FID to other organic structural categories also is a reflection of their primary combustion breakdown and a measure of the initial pool of unburned carbon. Exactly similar responses are seen in both the FID and in soot formation tendencies. The connection though is indirect in that both processes relate to and result from the same pool of non-oxidized carbon, rather than any implied inceptive role. As a result, the observed sensitivities previously recorded with the FID now can be a useful aid in validating the primary dominant steps in combustion mechanisms and the example of dimethyl ether combustion is used as an illustration. At present, this rich analytical database could be particularly useful in modeling the more complex partially oxygenated fuels that now are being extensively studied.     

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.     

An experimental and kinetic modeling study of cyclopentadiene pyrolysis: First growth of polycyclic aromatic hydrocarbons

The importance of 1,3-cyclopentadiene (CPD) and cyclopentadienyl (CPDyl) moieties in the growth of polycyclic aromatic hydrocarbons (PAHs) was studied using new experimental data and ab initio calculations. The experimental investigation was performed in a tubular continuous flow pyrolysis reactor under both high (24molN₂/molCPD)$(24{\text{mol}}_{{\text{N}}_2}/{\text{mol}}_{\text{CPD}})$ and low (5molN₂/molCPD)$(5{\text{mol}}_{{\text{N}}_2}/{\text{mol}}_{\text{CPD}})$ nitrogen dilutions, covering a temperature range of 873–1123 K, at a fixed pressure of 1.7 bara. At the most severe conditions up to 84% of CPD is converted, and the amount of PAHs is more than 65 wt%. Major products observed during CPD pyrolysis were benzene, indene, methyl-indenes and naphthalene, in line with previous studies. On-line GC × GC-FID/(TOF-MS) also allowed to quantify minor species (methane, toluene, styrene, phenanthrene, anthracene, etc.), never reported before at this level of accuracy. The new experimental data have been used to further analyze the role of the successive interactions of CPD, indene, and naphthalene as well as the recombination and addition reactions of their resonantly stabilized radicals and refine their kinetics. The results of the modeling study are in good agreement with existing and new experimental observations.     

Simulation of the influence of flue gas cleaning system on the energetic efficiency of a waste-to-energy plant

Municipal solid waste incinerators are designed to enhance the electrical efficiency obtained by the plant as much as possible. For this reason strong integration between the flue gas cleaning system and the heat recovery system is required. To provide higher electrical efficiencies acid gas neutralization process has the major importance in flue gas cleaning system. At least four technologies are usually applied for acid gas removal: dry neutralization with Ca(OH)₂ or with NaHCO₃, semi-dry neutralization with milk of lime and wet scrubbing. Nowadays, wet scrubbers are rarely used as a result of the large amount of liquid effluents produced; wet scrubbing technology is often applied as a final treatment after a dry neutralization. Operating conditions of the plant were simulated by using Aspen Plus in order to investigate the influences of four different technologies on the electrical efficiency of the plant. The results of the simulations did not show a great influence of the gas cleaning system on the net electrical efficiency, as the difference between the most advantageous technology (neutralization with NaHCO₃) and the worst one, is about 1%.     

废气再循环对二甲基醚均质压燃燃烧过程影响的试验研究

在一台单缸发动机上进行了废气再循环(EGR)对二甲基醚(DME)均质压燃(HCCI)燃烧过程影响的试验研究。结果表明,EGR比例小于20％对运行最大负荷工况范围影响不大;采用高比例EGR可以拓宽DME均质压燃运行工况范围,随着EGR率增大,HCCI运行的最大负荷工况增大,着火燃烧时刻推迟,燃烧放热率降低,缸内最大爆发压力降低,发动机热效率增大;EGR率小于75％,HC排放略有降低或相当,EGR率为75％时,HC排放显著增加;EGR率大于25％,随着EGR率增加,CO排放增大,小负荷工况尤其明显,在中高负荷工况,EGR率对CO排放影响较小。     

Numerical modeling and experimental study of the influence of GDL properties on performance in a PEMFC

This work is to study the effect of properties of gas diffusion layer (GDL) on performance in a polymer electrolyte membrane fuel cell (PEMFC) by both numerical simulation and experiments. The 1-dimension numerical simulation using the mixture-phase model is developed to calculate polarization curve. We are able to estimate optimum GDL properties for cell performance from numerical simulation results. Various GDLs which have different properties are prepared to verify accuracy of the simulation results. The contact angle and gas permeability of GDLs are controlled by polytetrafluoroethylene (PTFE) content in micro-porous layers (MPLs). MPL slurry is prepared by homogeneous blending of carbon powder, PTFE suspension, isopropyl alcohol and glycerol. Then the slurry is coated on gas diffusion mediums (GDMs) surface with controlled thickness by blade coating method. Non-woven carbon papers which have different thicknesses of 200 μm and 380 μm are used as GDMs. The prepared GDLs are measured by surface morphology, contact angle, gas permeability and through-plane electrical resistance. Moreover, the GDLs are tested in a 25 cm² single cell at 70 °C in humidified H₂/air condition. The contact angle of GDL increases with increasing PTFE content in MPL. However, the gas permeability and through-plane electrical conductivity decrease with increasing PTFE content and thickness of GDM. These changes in properties of GDL greatly influence the cell performance. As a result, the best performance is obtained by GDL consists of 200 μm thick non-woven carbon paper as GDM and MPL contained 20 wt.% PTFE content.     

二甲基醚（DME）燃烧特性研究

作者在定容燃烧弹上用火焰直接成像法研究二甲基醚 (DME)燃烧过程 ,研究了 DME的滞燃期和火焰传播特性以及不同环境温度和压力对燃烧过程的影响。研究结果表明 ,DME的滞燃期比柴油短 ,燃烧室内的温度和压力升高时 ,滞燃期缩短 ;DME的着火位置靠近喷嘴一侧 ,柴油与 DME的体积相同时 ,DME的燃烧持续期比柴油短 ;DME的燃烧火焰亮度比柴油小 ,表明 DME的燃烧温度比柴油低。燃烧后期 ,燃用 DME时 ,喷嘴有明显的泄漏现象。此外 ,作者在单缸直喷式柴油机上进行了燃用 DME的燃烧特性试验研究 ,研究结果表明 ,DME的预混合燃烧放热率比柴油低 ,缸内最大爆发压力和最大压力升高率比柴油低。由于喷油持续期延长 ,DME的燃烧持续期比柴油长 ,在上止点后 80° CA出现一个较大的放热峰值。     

EGR对直喷式柴油机冷起动过程着火燃烧的影响分析

通过在一台135单缸直喷柴油机上分别进行内部EGR（IEGR）、外部EGR（EEGR）条件下的冷起动试验,分析了内、外部EGR对柴油机冷起动过程着火燃烧性能及排放的影响。加入内、外部EGR后,由于EGR中含有大量的燃油蒸气、部分氧化产物等活性成分,初始着火循环的着火燃烧性能得到显著改善。在冷起动过程中,加入一定量的内部或外部EGR,有利于提高燃烧过程的稳定性。但过大的外部EGR量,将导致发动机燃烧极度不稳定甚至失火。由试验结果还可以看到,加入适当的内、外部EGR,均能有效地改善冷起动过程的烟度排放。对于NOx排放,当采用外部EGR方式时,有明显的改善作用;但当采用内部EGR方式时,由于残余废气的热效应,NOx排放随内部EGR量的增大而增大。     

Three-stage autoignition of gasoline in an HCCI engine: An experimental and chemical kinetic modeling investigation

The alternative HCCI combustion mode presents a possible means for decreasing the pollution with respect to conventional gasoline or diesel engines, while maintaining the efficiency of a diesel engine or even increasing it. This paper investigates the possibility of using gasoline in an HCCI engine and analyzes the autoignition of gasoline in such an engine. The compression ratio that has been used is 13.5, keeping the inlet temperature at 70 °C, varying the equivalence ratio from 0.3 to 0.54, and the EGR (represented by N₂) ratio from 0 to 37 vol%. For comparison, a PRF95 and a surrogate containing 11 vol% n-heptane, 59 vol% iso-octane, and 30 vol% toluene are used. A previously validated kinetic surrogate mechanism is used to analyze the experiments and to yield possible explanations to kinetic phenomena. From this work, it seems quite possible to use the high octane-rated gasoline for autoignition purposes, even under lean inlet conditions. Furthermore, it appeared that gasoline and its surrogate, unlike PRF95, show a three-stage autoignition. Since the PRF95 does not contain toluene, it is suggested by the kinetic mechanism that the benzyl radical, issued from toluene, causes this so-defined “obstructed preignition” and delaying thereby the final ignition for gasoline and its surrogate. The results of the kinetic mechanism supporting this explanation are shown in this paper.