Influence of wall heat loss on the emission characteristics of premixed ammonia-air swirling flames interacting with the combustor wall

The influence of wall heat loss on the emission characteristics of ammonia-air swirling flames has been investigated employing Planar Laser-Induced Fluorescence imaging of OH radicals and Fourier Transform Infrared spectrometry of the exhaust gases in combustors with insulated and uninsulated walls over a range of equivalence ratios, ?, and pressures up to 0.5 MPa. Strong influence of wall heat loss on the flames led to quenching of the flame front near the combustor wall at 0.1 MPa, resulting in large unburned NH₃ emissions, and inhibited the stabilization of flames in the outer recirculating zone (ORZ). A decrease in heat loss effects with an increase in pressure promoted extension of the fuel-rich stabilization limit owing to increased recirculation of H₂ from NH₃ decomposition in the ORZ. The influence of wall heat loss resulted in emission trends that contradict already reported trends in literature. NO emissions were found to be substantially low while unburned NH₃ and N₂O emissions were high at fuel-lean conditions during single-stage combustion, with values such as 55 ppmv of NO, 580 ppmv of N₂O and 4457 ppmv of NH₃ at ? = 0.8. In addition, the response of the flame to wall heat loss as pressure increased was more important than the effects of pressure on fuel-NO emission, thereby leading to an increase in NO emission with pressure. It was found that a reduction in wall heat loss or a sufficiently long fluid residence time in the primary combustion zone is necessary for efficient control of NH₃ and N₂O emissions in two-stage rich-lean ammonia combustors, the latter being more effective for N₂O in addition to NO control. This study demonstrates that the influence of wall heat loss should not be ignored in emissions measurements in NH₃-air combustion, and also advances the understanding of previous studies on ammonia micro gas turbines.     

Flame inhibition by phosphorus-containing compounds in lean and rich propane flames

Chemical inhibition of laminar propane flames by organophosphorus compounds has been studied experimentally and computationally using a detailed chemical kinetic reaction mechanism. Both fuel-lean and fuel-rich propane flames were studied to examine the role of equivalence ratio in flame inhibition. The experiments examined a wide variety of organophosphorus compounds. We report on experimental species flame profiles for tri-methyl phosphate (TMP) and compare them with modeled species flame profile results of TMP and di-methyl methyl phosphonate (DMMP). Both experiments and kinetic modeling indicate that inhibition efficiency is effectively the same for all of the organophosphorus compounds examined, independent of the molecular structure of the initial inhibitor molecule. Chemical inhibition is due to reactions involving small P-bearing species HOPO₂ and HOPO produced by the organophosphorus compounds (OPCs). Ratios of HOPO₂ and HOPO concentrations differ between lean and rich flames, with HOPO₂ dominant in lean flames while HOPO dominates in rich flames. Resulting HOPO₂ and HOPO species profiles do not significantly depend on the initial source of the HOPO₂ and HOPO, and thus are relatively insensitive to the initial OPC inhibitor. A more generalized form of the Twarowski mechanism is developed to account for the results observed, and new theoretical values are determined for heats of formation of the important P-containing species, using the BAC-G2 method.     

Experimental study of influence of temperature on fuel-N conversion and recycle NO reduction in oxyfuel combustion

Coal combustion in O₂/CO₂ environment was examined with a bituminous coal in which the gas-phase and char combustion stages were considered separately. The effects of temperature (1000–1300 °C) and the excess oxygen ratio λ (0.6–1.4) on the conversion of volatile-N and char-N to NOx were studied. Also, the reduction of recycle NOx by fuel-N was investigated under various conditions. The results show that fuel-N conversion to NO in O₂/CO₂ is lower than that in O₂/N₂. In O₂/CO₂ atmosphere, the volatile-N conversion ratios vary from 1–7% to 15–24% under fuel-rich and fuel-lean conditions, respectively. The char-N conversion ratios are 11–28% and 30–50% under fuel-rich and fuel-lean conditions, respectively. The influences of temperature on the conversion of volatile-N to NO under fuel-rich and fuel-lean conditions are contrary. A significant difference for char-N conversion in fuel-rich and fuel-lean conditions is observed. The experimental data of recycle NO reduction indicate that the reduction of recycle NO by gas-phase reaction can be enhanced by volatile-N addition in fuel-lean condition at high temperature, while in fuel-rich condition, the volatile-N influence cancelled out and the overall impact is small. NO/char reaction competes with the conversion of fuel-N to NO at higher temperatures.     

Laser-induced fluorescence detection of acetylene in low-pressure propane and methane flames

Laser-induced fluorescence is used to detect and record profiles of acetylene formed as an intermediate species in 10-Torr premixed propane and methane flames. In low-temperature regions of the flames, excitation spectra confirm acetylene as the spectral carrier. The spectra of acetylene overlap those of O₂ and NO in terms of both excitation and detection wavelengths, however, acetylene can be detected with relatively little interference in the vicinity of 228 nm, using a detection wavelength of 260 nm. The fluorescence lifetime of acetylene in the flame conditions studied is approximately 20 ns, much shorter than the radiative lifetime, due to a high quenching rate for all the colliders investigated. This can be exploited in low-pressure flames to avoid interference from acetylene in monitoring nitric oxide. The acetylene mole fraction in propane flames reaches its peak value at nearly the same location as that of HCO, slightly closer to the burner than the peak CH mole fraction. The acetylene fluorescence signal is easily detected in propane flames over equivalence ratios from 0.6 to 1.2, although it increases under fuel-rich conditions. In methane flames, the acetylene signal is much weaker and is undetectable for fuel-lean conditions. Received: 5 August 2002 / Revised version: 30 September 2002 / Published online: 20 December 2002 RID="*" ID="*"Corresponding author. Fax: +1-202/767-1716, E-mail: brad@code6185.nrl.navy.mil     

Tomographic reconstruction of the OH*-chemiluminescence distribution in premixed and diffusion flames

A fast tomographic reconstruction device has been developed to detect the two-dimensional distribution of the chemiluminescence of OH^* in the reaction zones of flames. In the set-up, special emphasis was placed on the applicability of the technique to turbulent flames. A spatial resolution of the system, <1–2 mm, and an exposure time of 100–200 μs are required to resolve the chemiluminescence signal of OH^* originating from the folded flame front of a turbulent flame.     

The effect of hydrogen addition on flammability limit and NOx emission in ultra-lean counterflow CH4/air premixed flames

The effect of hydrogen addition to ultra lean counterflow CH₄/air premixed flames on the extinction limits and the characteristics of NO_x emission was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. The results show that the addition of hydrogen can significantly enlarge the flammable region and extend the flammability limit to lower equivalence ratios. If the equivalence ratio is kept constant, the addition of hydrogen increases the emission of NO in a flame due to the enhancement in the rate of the NNH or N₂O intermediate NO formation routes. The addition of hydrogen causes a monotonic decrease in the formation of NO₂ and N₂O, except flames near the extinction limits, where the emission of NO₂ and N₂O first increases, and then decreases with the increase in the fraction of hydrogen. Overall, hydrogen enrichment technology allows stable combustion under ultra lean conditions, resulting in significant CO₂ and NO emission reduction.     

Experimental study on co-firing characteristics of ammonia with pulverized coal in a staged combustion drop tube furnace

Utilizing ammonia as a co-firing fuel to replace amounts of fossil fuel seems a feasible solution to reduce carbon emissions in existing pulverized coal-fired power plants. However, there are some problems needed to be considered when treating ammonia as a fuel, such as low flame stability, low combustion efficiency, and high NO_x emission. In this study, the co-firing characteristics of ammonia with pulverized coal are studied in a drop tube furnace with staged combustion strategy. Results showed that staged combustion would play a key role in reducing NO_x emissions by reducing the production of char-NO_x and fuel(NH₃)-NO_x simultaneously. Furthermore, the effects of different ammonia co-firing methods on the flue gas properties and unburned carbon contents were compared to achieve both efficient combustion and low NO_x emission. It was found that when ammonia was injected into 300 mm downstream under the condition of 20% co-firing, lower NO_x emission and unburnt carbon content than those of pure coal combustion can be achieved. This is probably caused by a combined effect of a high local equivalence ratio of NH₃/air and the prominent denitration effect of NH₃ in the vicinity of the NH₃ downstream injection location. In addition, NO_x emissions can be kept at approximately the same level as coal combustion when the co-firing ratio is below 30%. And the influence of reaction temperature on NO_x emissions is closely associated with the denitration efficiency of the NH₃. Almost no ammonia slip has been detected for any injection methods and co-firing ratio in the studied conditions. Thus, it can be confirmed that ammonia can be used as an alternative fuel to realize CO₂ reduction without extensive retrofitting works. And the NO_x emission can be reduced by producing a locally NH₃ flame zone with a high equivalence ratio as well as ensuring adequate residence time.     

Flame studies of C2 hydrocarbons

The oxidation characteristics of C₂ hydrocarbons were revisited in flames established in the counterflow configuration. Laminar flame speeds of ethane/air, ethylene/air, and acetylene/oxygen/nitrogen mixtures as well as extinction strain rates of non-premixed ethane/air flames were measured using digital particle image velocimetry. The experiments were modeled using three different kinetic models. While the experimental and computed laminar flame speeds agreed closely for all C₂ hydrocarbons under fuel-lean conditions, notable discrepancies were identified under fuel-rich conditions. Using the computed flame structures, insight was provided into the controlling mechanisms that could be responsible for the observed discrepancies. More specifically, the uncertainties associated with the kinetics of the thermal decomposition of the ethyl radical were found to be a potential source of the observed discrepancies for ethane flames. It was shown also by using alternative rate constants for the ethyl radical decomposition, the rate of flame propagation and the extinction propensity are affected notably. Furthermore, the values of the branching ratio of acetylene consumption reactions involving atomic oxygen were found to have a significant effect on the propagation of rich acetylene flames.     

Insight into the inner structure of stretched premixed ammonia-air flames

Ammonia as a fuel has sparked significant interest in the combustion community. Although, using ammonia has a lot of advantages including no carbon emissions, ammonia-air flames are characterized as thick flames with low flame speeds. It is important to understand the flame structure to know the combustion process better. Flame thickness is an important property of the flame which characterizes the reactivity of the flame. Identifying the preheat zone is necessary to determine the fresh gas surface which is used to determine flame speed. Also, understanding the behavior of the important species emitted helps to demonstrate the reaction pathway which may be implemented in chemical kinetics schemes. Further, it is interesting to know the effect of curvature on the emission of excited species which gives direct knowledge on the influence of curvature on the flame reactivity. It was seen that the change in reactivity was manifested as a change in thickness of the species. The experiments presented here were performed on a Bunsen burner at atmospheric conditions. The laminar flame speeds have been evaluated over a range of equivalence ratios by choosing the isotherm as specified by the definition of the flame speed which are slightly higher than the values obtained from the literature. Chemiluminescence from NH* and NH₂* was studied for different equivalence ratios. A 1D simulation performed in Chemkin-Pro-was used to compare the behavior of the counterpart non-excited species. This comparison helps to correlate excited and non-excited species and also to define the structure of the ammonia-air flame. Both NH* and NH₂* have been determined as heat release rate markers.     

Effects of pressure on flame propagation in a premixture containing fine fuel droplets

Combustion experiments on fuel droplet–vapor–air mixtures have been performed with a rapid expansion apparatus which generates monodispersed droplet clouds with narrow diameter distribution using the condensation method. The effects of fine fuel droplets on flame propagation were investigated for ethanol droplet–vapor–air mixtures at various pressures from 0.2 to 1.0 MPa. A stagnant fuel droplet–vapor–air mixture, generated in a rapid expansion chamber, was ignited at the center of the chamber using an ignition wire. Spherical flame propagation under constant-pressure conditions was observed with a high-speed video camera and flame speed was measured. Total equivalence ratio, and the ratio of liquid fuel mass to total fuel mass, was varied from 0.6 to 1.4 and from zero to 56%, respectively. The mean droplet diameter of fuel droplet–vapor–air mixtures was set at 8.5 and 11 μm. It was found that the flame speed of droplet–vapor–air mixtures less than 0.9 in the total equivalence ratio exceeds that of premixed gases of the same total equivalence ratio at all pressures. The flame speed of fuel droplet–vapor–air mixtures decreases as the pressure increases in all total equivalence ratios. At large ratios of liquid fuel mass to total fuel mass, the normalized flame speed (the flame speed of droplet–vapor–air mixtures divided by the flame speed of the premixed gas with the same total equivalence ratio), increases with the increase in pressure for fuel-lean mixtures, and it decreases for fuel-rich mixtures. The outcome is reversed at small ratios of liquid fuel mass to total fuel mass; the normalized flame speed decreases with the increase in pressure for fuel-lean mixtures, and increases for fuel-rich mixtures. The results suggest that the increase in pressure promotes droplet evaporation in the preheat zone.     

Effects of radiation heat loss on laminar premixed ammonia/air flames

Ammonia (NH₃) direct combustion is attracting attention for energy utilization without CO₂ emissions, but fundamental knowledge related to ammonia combustion is still insufficient. This study was designed to examine effects of radiation heat loss on laminar ammonia/air premixed flames because of their very low flame speeds. After numerical simulations for 1-D planar flames with and without radiation heat loss modeled by the optically thin model were conducted, effects of radiation heat loss on flame speeds, flame structure and emissions were investigated. Simulations were also conducted for methane/air mixtures as a reference. Effects of radiation heat loss on flame speeds were strong only near the flammability limits for methane, but were strong over widely diverse equivalence ratios for ammonia. The lower radiative flame temperature suppressed the thermal decomposition of unburned ammonia to hydrogen (H₂) at rich conditions. The equivalence ratio for a low emission window of ammonia and nitric oxide (NO) in the radiative condition shifted to a lower value than that in the adiabatic condition.     

Effects of fine fuel droplets on a laminar flame stabilized in a partially prevaporized spray stream

A partially prevaporized spray burner was developed to investigate the interaction between fuel droplets and a flame. Monodispersed partially prevaporized ethanol sprays with narrow diameter distribution were generated by the condensation method using rapid pressure reduction of a saturated ethanol vapor–air mixture. A tilted flat flame was stabilized at the nozzle exit using a hot wire. Particle tracking velocimetry (PTV) was applied to measurements of the droplet velocity; the laminar burning velocity was obtained from gas velocity derived from the droplet velocity. Observations were made of flames in partially prevaporized spray streams with mean droplet diameters of 7 μm and the liquid equivalence ratios of 0.2; the total equivalence ratio was varied. In all cases, a sharp vaporization plane was observed in front of the blue flame. Flame oscillation was observed on the fuel-rich side. At strain rates under 50 s⁻¹, the change in the burning velocity with the strain rate is small in fuel-lean spray streams. In spray streams of 0.7 and 0.8 in the total equivalence ratio, burning velocity increases with strain rates of greater than 50 s⁻¹. However, in spray streams with 0.9 and 1.0 in the total equivalence ratio, burning velocity decreases as the strain rate increases. At strain rates greater than 80 s⁻¹, burning velocity decreases with an increased gas equivalence ratio. The effect of mean droplet diameter, and the entry length of droplets into a flame on the laminar burning velocity, were also investigated to interpret the effect of the strain rate on the laminar burning velocity of partially prevaporized sprays.     

Laminar flame speed and autoignition characteristics of surrogate jet fuel blended with hydrogen

Hydrogen combustion has emerged as one promising option toward the achievement of carbon-neutral in aviation. In this study, the effects of hydrogen addition on laminar flame speeds, autoignition, and the coupling of autoignition and flame propagation for surrogate jet fuel n-dodecane are numerically investigated at representative engine conditions to elucidate the potential challenges for flame stabilization and the autoignition risks in combustor design. Results show that the normalized flame speed increases almost linearly with hydrogen addition for fuel-lean conditions, while for fuel-rich conditions it increases nonlinearly and can be up to 20. This poses great challenges for avoiding flameholding and flashback, particularly for fuel-rich mixtures. Results further show that flame speed enhancement due to the increased flame temperature can be neglected under fuel-lean conditions, but not for fuel-rich mixtures. For the dependence of ignition delay time on temperature, there exists a unique intersection between pure n-dodecane/air and H₂/air mixtures. Near the intersection temperature, there exists subtle kinetic coupling of the two fuels, leading to different H₂ roles, e.g., accelerator or inhibitor, for the autoignition process of n-dodecane/H₂/air mixtures. With this intersection temperature, the diagram for autoignition risks is constructed, which demonstrates that H₂ acts as an inhibitor under subsonic cruise conditions while either an inhibitor or an accelerator under supersonic cruise conditions depending on the combustor inlet temperature and the amount of hydrogen addition. With the potential coupling of autoignition and flame propagation, the 1-D autoignition-assisted flame calculations show that hydrogen addition can alleviate or even eliminate the two-stage ignition characteristics for pure n-dodecane/air flames. For n-dodecane blended with hydrogen, the autoignition-assisted flame propagation speed, as well as the global transition from flame propagation to autoignition, can still be described by an analytic scaling parameterized by the ignition Damkӧhler number.     

气化炉内柴油火焰光谱辐射特性及CH*二维辐射特性研究

火焰的自发辐射光谱与火焰的结构、温度分布等燃烧特征参数密切相关。对激发态自由基辐射的辐射强度与二维分布进行研究,可清晰地反映火焰燃烧状态而不对火焰产生扰动。基于多喷嘴对置式气流床气化实验平台,利用光纤光谱仪和配置CCD相机的高温内窥镜,对柴油扩散火焰的辐射光谱及CH*辐射二维分布特性进行研究。考察了当量比和撞击作用对火焰辐射光谱和CH*辐射分布的影响。结果表明,柴油火焰在306.47及309.12 nm处存在OH*辐射特征峰,在431.42 nm处存在CH*辐射特征峰,且存在明显的碱金属原子Na*(589.45 nm),K*(766.91和770.06 nm)发射光谱。此外,由于柴油不完全燃烧生成大量碳黑,在辐射光谱的可见光波段产生了强烈的连续黑体辐射。火焰中的黑体辐射对CH*辐射特征峰的检测存在干扰,且当量比越低时背景辐射越强,对自由基特征峰检测干扰越大。基于普朗克定律利用插值法可扣除430 nm附近波段背景辐射。柴油火焰中CH*辐射峰值随当量比的增加单调减小,CH*辐射等值线沿火焰发展方向依次出现三峰状、双峰状及单峰状,最终收缩为以反应核心区为中心的圆核。随着当量比的提高,出现各个形状的CH*辐射强度阈值不断降低,火焰主反应区面积减小且向下游移动,当量比增加到1.0附近时,理论上柴油完全燃烧,CH*辐射强度显著降低,贫燃火焰的CH*辐射强度及分布区域几乎稳定不变。利用CH*辐射强度值判定火焰举升长度,对于单喷嘴射流火焰,火焰举升长度随当量比的增加经历了显著增加后小幅下降的过程。相同当量比时两喷嘴撞击火焰CH*辐射强度峰值始终高于单喷嘴射流火焰对应值;火焰举升长度随当量比的增加小幅增加。火焰撞击的约束作用使得火焰举升长度不易随着当量比变化发生较大波动,燃烧更加稳定。这为定量判断火焰燃烧状态提供了一种直观、有效的方法,同时为柴油燃烧的化学动力学研究提供了实验依据。     

Experimental and kinetic modeling study of the positive ions in premixed ethylene flames over a range of equivalence ratios

Understanding the ion chemistry in flames is crucial for developing ion sensitive technologies for controlling combustion processes. In this work, we measured the spatial distributions of positive ions in atmospheric-pressure burner-stabilized premixed flames of ethylene/oxygen/argon mixtures in a wide range of equivalence ratios ϕ = 0.4÷1.5. A flame sampling molecular beam system coupled with a quadrupole mass spectrometer was used to obtain the spatial distributions of cations in the flames, and a high mass resolution time-of-flight mass spectrometer was utilized for the identification of the cations having similar m/z ratios. The measured profiles of the flame ions were corrected for the contribution of hydrates formed during sampling in the flames slightly upstream the flame reaction zone. We also proposed an updated ion chemistry model and verified it against the experimental profiles of the most abundant cations in the flames. Our model is based on the kinetic mechanism available in the literature extended with the reactions for C₃H₅⁺ cation. Highly accurate W2-F12 quantum chemical calculations were used to obtain a reliable formation enthalpy of C₃H₅⁺. The model was found to reproduce properly the measured relative abundance of the key oxygenated cations (viz., CH₅O⁺, C₂H₃O⁺) in the whole range of equivalence ratios employed, and the C₃H₅⁺ cation abundance in the richest flame with ϕ=1.5, but significantly underpredicts the relative mole fraction of C₃H₃⁺, which becomes a key species under fuel-rich conditions. Apart from this, several aromatic and cyclic C_xH_y cations dominating under fuel-rich conditions were identified. We also considered the most important directions for the further refinement of the mechanism.     

A structural study of premixed hydrogen-air cellular tubular flames

Two dimensionally spatially resolved structural measurements are reported for cellular phenomena in lean laminar premixed hydrogen-air tubular flames. Laser-induced Raman scattering and chemiluminescence imaging are combined to investigate low Lewis number lean hydrogen-air flames. The strong effect of thermal-diffusive imbalance is observed in radial profiles interpolated through the centers of reaction and extinction zones. In the flame cell, the equivalence ratio is ～80% higher than the inlet mixture, resulting in a peak flame temperature of 1600 K that is 550 K above the adiabatic flame temperature of the inlet mixture (1055 K). In the adjacent extinction zone, the temperatures are ～900 K lower than the peak flame temperature and the equivalence ratio is similar to the inlet mixture. Despite doubling the global stretch rate from 200 s^?1 to 400 s^?1, the enhancement of local equivalence ratio and peak temperature in the flame cell remain similar. This enhancement seems dependent on the local cellular flame curvature, that is similar between both cases. With strong preferential diffusion effects, cellular flames offer unique validation data to improve the accuracy of current molecular transport modeling techniques.     

Experimental study of signal trapping of OH laser induced fluorescence and chemiluminescence in flames

The absorption of OH^∗ chemiluminescence and laser-induced fluorescence (LIF) in the exhaust gas of confined premixed laminar CH₄/air flames at atmospheric pressure was investigated. One flame was used as source and a second as absorber. OH LIF was excited in the ν″=0→ν′=1 band of the A–X electronic system around ≈283 nm and spectrally resolved detected in the (0,0) and (1,1) vibrational bands around 305–320 nm. For OH^∗ chemiluminescence, spectrally resolved detection was performed in the wavelength range 280–340 nm. For an absorption path of 54 mm and at T≈2000 K, signal trapping on the order of 10–40% was observed. Signal trapping was most pronounced in the (0,0) band, as expected from the thermal population distribution of OH in the electronic ground state. The spectral distribution of the signals and the wavelength dependence of the signal trapping are addressed in this paper. Implications from the results with respect to detection strategies and chemiluminescence-based equivalence ratio measurements are discussed.     

Addition of NO2 to a laminar premixed ethylene-air flame: Effect on soot formation

Experiments were conducted on a laminar premixed ethylene-air flame at equivalence ratios of 2.34 and 2.64. Comparisons were made between flames with 5% NO₂ added by volume. Soot volume fraction was measured using light extinction and light scattering and fluorescence measurements were also obtained to provide added insight into the soot formation process. The flame temperature profiles in these flames were measured using a spectral line reversal technique in the non-sooting region, while two-color pyrometry was used in the sooting region. Chemical kinetics modeling using the PREMIX 1-D laminar flame code was used to understand the chemical role of the NO₂ in the soot formation process. The modeling used kinetic mechanisms available in the literature. Experimental results indicated a reduction in the soot volume fraction in the flame with NO₂ added and a delay in the onset of soot as a function of height above the burner. In addition, fluorescence signals—often argued to be an indicator of PAH—were observed to be lower near the burner surface for the flames with NO₂ added as compared to the baseline flames. These trends were captured using a chemical kinetics model that was used to simulate the flame prior to soot inception. The reduction in soot is attributed to a decrease in the H-atom concentration induced by the reaction with NO₂ and a subsequent reduction in acetylene in the pre-soot inception region.