Effect of N2/CO2 dilution on laminar burning velocity of H2–air mixtures at high temperatures

The laminar burning velocities of H₂–air mixtures diluted with N₂ or CO₂ gas at high temperatures were obtained from planar flames observed in externally heated diverging channels. Experiments were conducted for an equivalence ratio range of 0.8–1.3 and temperature range of 350–600 K with various dilution rates. In addition, computational predictions for burning velocities and their comparison with experimental results and detailed flame structures have been presented. Sensitivity analysis was carried out to identify important reactions and their contribution to the laminar burning velocity. The computational predictions are in reasonably good agreement with the present experimental data (especially for N₂ dilution case). The burning velocity maxima was observed for slightly rich mixtures and this maxima was found to shift to higher equivalence ratios (Ф) with a decrease in the dilution. The effect of CO₂ dilution was more profound than N₂ dilution in reducing the burning velocity of mixtures at higher temperatures.     

Laminar burning velocities and flame characteristics of CO–H2–CO2–O2 mixtures

Laminar burning velocities of CO–H₂–CO₂–O₂ flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO₂ on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H₂–CO₂–O₂ mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO₂ fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO₂ fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO₂ fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO₂ fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO₂ in the flame. The CO₂ acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O₂ = O + OH, CO + OH = CO₂ + H and H + O₂(+M) = HO₂(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO₂ fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.     

Laminar burning velocity of lean H2–CO mixtures at elevated pressure using the heat flux method

Laminar burning velocity measurements of 50:50 and 85:15% (by volume) H₂–CO mixtures with O₂–N₂ and O₂–He oxidizers were performed at lean conditions (equivalence ratio from 0.5 to 1) and elevated pressures (1 atm–9 atm). The heat flux method (HFM) is employed for determining the laminar burning velocity of the fuel–oxidizer mixtures. HFM creates a one-dimensional adiabatic stretchless flame which is an important prerequisite in defining the laminar burning velocity. This technique is based on balancing the heat loss from the flame to the burner with heat gain to the unburnt gas mixture, in a very simple way, such that no net heat loss to the burner is obtained. Instabilities are observed in lean H₂–CO flames with nitrogen as the bath gas for pressures above 4 atm. Stable flames are obtained with helium as the bath gas for the entire pressure range. With the aim to cater stringent conditions for combustion systems such as gas turbines, an updated H₂–CO kinetic mechanism is proposed and validated against experimental results. The scheme was updated with recent rate constants proposed in literature to suit both atmospheric and elevated pressures. The proposed kinetic model agrees with new experimental results. At conditions of high pressure and lean combustion, reactions H + O₂ = OH + O and H + O₂ (+M) = H₂ (+M) compete the most when compared to other reactions. Reaction H + HO₂ = OH + OH contributes to OH production, however, less at high-pressure conditions. At higher CO concentrations and leaner mixtures an important role of reaction CO + OH = CO₂ + H is observed in the oxidation of CO.     

The chemistry involved in the third explosion limit of H2–O2 mixtures

The third explosion limit of hydrogen oxidation in closed vessels has always been thought to be the result of the competition between homogeneous gas-phase reactions and diffusion of hydroperoxyl radicals to the walls, where they are destroyed. It has recently been observed that this species actually follows a chemical-kinetic steady state in this regime, with the consequence that its diffusive rate toward the catalytic walls becomes irrelevant. Here we show that the critical explosion conditions are determined instead by the fate of hydrogen peroxide, which emerges as the controlling reactant for the resulting gas-phase chemistry. A simple, accurate analytic expression for the third explosion limit follows from identification of the critical conditions for existence of weakly reactive, diffusion–reaction solutions, thereby providing the answer to a long-standing problem that in early work was characterized as being hopelessly difficult.     

Effects of N2O addition on the ignition of H2–O2 mixtures: Experimental and detailed kinetic modeling study

Ignition delay times of H₂/O₂ mixtures highly diluted with Ar and doped with various amounts of N₂O (100, 400, 1600, 3200 ppm) were measured in a shock tube behind reflected shock waves over a wide range of temperatures (940–1675 K). The pressure range investigated during this work (around 1.6, 13 and 32 atm) allows studying the effect of N₂O on hydrogen ignition at pressure conditions that have never been heretofore investigated. Ignition delay times were decreased when N₂O was added to the mixture only for the higher nitrous oxide concentrations, and some changes in the activation energy were also observed at 1.5 and 32 atm. When it occurred, the decrease in the ignition delay time was proportional to the amount of N₂O added and depended on pressure and temperature conditions. A detailed chemical kinetics model was developed using kinetic mechanisms from the literature. This model predicts well the experimental data obtained during this study and from the literature. The chemical analysis using this model showed that the decrease in the ignition delay time was mainly due to the reaction N₂O + M ? N₂ + O + M which provides O atoms to strengthen the channel O + H₂ ? OH + H.     

Combustion characteristics of an SI engine fueled with H2–CO blended fuel and diluted by CO2

This paper presents further results of the study on fundamental combustion characteristics of gaseous fuels simulated for a biogas produced through a biomass gasification process with a catalyzer. The main work focuses on combustion characteristics of H₂–CO blended fuel and the effect of CO₂ dilution on it in a spark-ignition engine under the condition of WOT, MBT and a constant speed of 1500 rpm. Equivalence ratio were limited to lower than 0.8 in order to avoid excessive high combustion temperature to damage the engine, and lean conditions were maintained during the experiment to get acceptable economy and emissions. The results show that the BMEP decreases with an increase in dilution rate. The COV of IMEP is lower than 10% under most conditions, while H₂ and CO₂ have the opposite influence on brake thermal efficiency. CO₂ dilution combustion could induce to remarkable decreasing in NO_x emission with little decrease in brake thermal efficiency, which benefits for biomass gaseous fuel application. If 500 ppm of NO_x emission and 26% of brake thermal efficiency could be viewed as accepted level, the accepted operation range of H₂–CO mixture have been obtained.     

The retardation kinetics of magnetite reduction using H2 and H2–H2O mixtures

Cylindrical compacts of magnetite were isothermally reduced at 773–1273 K with pure H₂ or H₂–H₂O mixtures. The initial reduction rates increased with temperature and partial pressures of H₂ in the H₂–H₂O mixtures. However, with progressing reduction, a dense iron layer formed around the wüstite grains and the rate significantly reduced. In this regime, solid state oxygen diffusion through the dense iron layer was rate limiting. This retardation of reduction occurred at degrees of reduction of 51–89%, depending on the temperature and H₂ partial pressure, which has a linear relationship with the dimensionless kinetic parameter, k₁^mixed/k₂^mixed, (k₁^mixed, k₂^mixed: contribution of gaseous mass transport (GMT) and interfacial chemical reaction (ICR) to the reduction rate, respectively) in the reaction-regime controlled by a combination of both mechanisms. However, under certain conditions (H₂, H₂–10%H₂O, 773 K//H₂–10, 20%H₂O, 873 K//H₂–20%H₂O, 973 K) the retardation was absent because of the formation of a microporous iron layer product.     

Hydrogen permeation and recovery from H2–N2 gas mixtures by Pd membranes with high permeance

Hydrogen separation from H₂–N₂ gas mixtures by means of high-permeance Pd membranes is an appropriate route to gain pure hydrogen for fuel cell applications. To figure out the mass transfer phenomena of H₂ in membrane tubes, H₂ permeation and recovery characteristics of two high-permeance Pd membranes are investigated. Four important factors influencing H₂ permeation, namely, the H₂ pressure difference, H₂ concentration, the flow rate at the exit of the retentate side, and membrane temperature, are taken into account. The experimental results suggest that decreasing H₂ concentration, flow rate, and temperature reduce the permeances of the membranes and H₂ recovery, even though the H₂ pressure difference is identical. The dimensionless permeance, a permeance ratio between H₂–N₂ gas mixture and pure H₂ as feed gases, is used to evaluate the extent of concentration polarization. Within the investigated ranges of the four factors, the dimensionless permeances of the two membranes are in the ranges of 0.022–0.206 and 0.042–0.359, respectively, revealing that the concentration polarization diminishes the permeance of the membranes down to the level within two orders of magnitude. Nevertheless, over 46% of H₂ is recovered.     

A new weighted-sum-of-gray-gases model for CO2–H2O gas mixtures

Decoupled radiative transfer calculations of Sandia Flame D are performed employing experimental measurements of temperature and gas compositions and the discrete ordinates method. Turbulence radiation interactions are accounted for employing temperature variance measurements. The spatial variations in the mean H₂O/CO₂ ratios within the flame are seen to vary widely and sometimes fall outside the range of the weighted-sum-of-gray-gases model (WSGGM) parameters reported in the literature. Therefore, parameters for a new WSGGM are computed from total emissivity correlations encompassing the range of the H₂O/CO₂ ratios encountered within the flame. Predictions from the new model compare favorably against the spectral-line-based WSGGM and existing benchmarks.     

Detonation propagation characteristic of H2–O2–N2 mixture in tube and effect of various initial conditions on it

As for the premixed H₂–O₂–N₂ gas ignited and induced by flame in tube, this paper represents systemic researches on its detonative formation process and flow field changes under different initial conditions (pressure, temperature, component concentration). The conservational Euler equation set with chemical reaction is taken as the basic gas phase equation model and the reduced elementary chemical reaction and shock wave problem are considered available so as to establish a theoretical model of premixed H₂–O₂–N₂ combustible gas detonation process. A unity coupling TVD format with second-order accuracy is adopted to solve the gas phase equation and deduce the two-dimension Riemann invariant, and the TVD format for solution of the polycomponent convection equation with elementary chemical reaction is proposed. Meanwhile, a time splitting format is adopted to perfectly treat with the rigid problem resulted from the higher time difference value between gas phase flow characteristic time and chemical reaction characteristic time. It is shown by the calculation results that the detonation waves form certain angle with relation to the tube wall surface at the initial stage of ignition, so as to incur reflections and form reflection waves; during the propagation of the detonation waves, the reflection wave structures are propagated backwards the back of waves constantly, so the whole flow field is characterized of obvious two-dimension. Besides, the excessive pressure detonation occurs at first before formation of the stable detonation propagation process, then a stable detonation propagation process forms finally. Mixed gas detonation characteristics resulted from different calculated-initially parameters are different. The higher the initial temperature and pressure of flame is, the shorter the induction time for detonation formed due to combustion acceleration of the mixed gas is, but which nearly brings no great influence on the later propagation process of the detonation waves. The initial mixed gas component can influence the detonation characteristic of the mixed gas observably, when the quantity relative ratio is close to 1 and the mixed gas with larger reaction activity, its detonation propagation speed is rapider and the pressure after detonation waves is higher. The simulation result keeps accordant with the calculated result of the typical C–J detonation theory model.     

O2/CO2和O2/N2氛围下煤粉富氧燃烧数值模拟

在目前煤炭依然作为能源主体的背景下,控制燃煤污染物排放有着重要意义。基于CFD数值模拟,建立伴流燃烧器模型,控制燃料、氧化剂入口流量恒定,设计了O₂/CO₂、O₂/N₂氧化剂氛围中O₂浓度在21%～40%内的多种工况,对煤粉燃烧特性及燃烧产生的污染物进行了研究。分析了不同工况下煤粉燃烧的温度分布、燃烧速率、碳烟、NO_x的生成情况。结果显示,在O₂/CO₂、O₂/N₂两种氧化剂氛围中,随着O₂浓度的上升,煤粉燃烧温度升高、燃烧速率增大,碳烟生成量均增加,同等O2浓度条件下,O₂/CO₂氛围的煤粉燃烧温度和燃烧速率均高于O₂/N₂氛围,碳烟生成量小于O₂/N₂氛围,且O₂/CO₂...     

O2/N2和O2/CO2气氛下煤半焦-生物质的混燃特性及影响因素

为掌握煤半焦与生物质在O₂/N₂和O₂/CO₂条件下的混燃特性及其影响因素,采用全自动物理化学吸附仪获得了煤半焦-生物质混合燃料的孔隙结构,采用热重实验分析了两种燃料的混燃特性和反应动力学,通过多元线性回归法研究了燃料比、比表面积与混燃特性参数之间的关系。结果表明,O₂/N₂气氛下,掺混生物质可改善煤半焦的着火、燃尽及综合燃烧特性;O₂/CO₂气氛下,掺混生物质能改善煤半焦的着火特性,但会延迟其燃尽。混燃的活化能在低温区和高温区有显著差异,生物质掺混比增大,两个温区的活化能都降低;两种气氛下,低温区的活化能相近,但O₂/CO₂气氛下高温区的活化能显著高于O₂/N₂气氛下的。O₂/N₂气氛下孔隙结构对燃烧特性的影响更显著,而O₂/CO₂气氛下...     

Another view of the upper and intermediate explosion limits of a H2–O2 system

In the present note we consider the two simultaneous mechanisms that are dominated by gas-phase reactions, namely the upper and intermediate explosion limits, and show that by employing the Le-Chatelier rule, a unified explosion limit is obtained in the form of a single analytical expression.     

Catalytic partial oxidation of CH4–H2 mixtures over Ni foams modified with Rh and Pt

The catalytic partial oxidation (CPO) of methane–hydrogen mixtures in air, intended for the first stage of hybrid radiant catalytic burners, was investigated under self-sustained short contact time conditions on commercial Ni foam catalysts eventually modified with Rh and Pt. The modified catalysts were prepared by a simple novel method based on the spontaneous deposition of noble metals via metal exchange reactions onto those Ni foam substrates. SEM-EDS, electrochemical methods and H₂-TPR analysis were integrated to characterize morphology, surface area of metal deposits and reducibility of foam catalysts before and after exposure to severe conditions in the CPO reactor. In particular Rh forms finely dispersed deposits that retain their high specific surface area at temperatures up ca. 1100 °C. Modification with noble metals enhances stability and reducibility of the Ni foam whereas the overall CPO performance is not significantly improved. Safe operation of the CPO reactor with up to 70% vol. H₂ in the fuel mixture has been achieved by properly increasing the feed equivalence ratio to avoid catalyst overheating, while guaranteeing high methane conversions and a persistent net hydrogen production.     

O2/CO2/H2O气氛下CO燃烧机理的分子动力学模拟研究

采用反应分子动力学(ReaxFF MD)模拟方法研究了O₂/CO₂/H₂O气氛下CO的燃烧。结果表明：根据化学平衡原理,高浓度CO₂抑制CO的氧化,同时CO₂在高温下参与反应CO₂+H—→CO+OH,进一步抑制CO氧化。在较低温度条件下,较高浓度H₂O的三体效应显著,抑制了CO氧化。另一方面,在较高温度条件下,H₂O参与的H₂O+H—→H₂+OH和H₂O+O—→OH+OH反应占据其化学作用的主导地位,进而促进CO氧化。随着O₂浓度的增加,CO的氧化速度加快。     

Effects of Fe substitutions by Ni in La–Ni–O perovskite-type oxides in reforming of methane with CO2 and O2

LaNiO₃ and LaNi_1−xFe_xO₃ (x = 0.2, 0.4, 0.6, 0.8 and 1) perovskites were prepared by the citrate sol–gel method. The prepared compounds were characterized by using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), temperature programmed reduction (TPR), and inductively coupled plasma (ICP) techniques. Specific surface area of the samples was measured by BET method. Morphology study of the prepared catalysts was performed using scanning and transmission electron microscopy (SEM and TEM, respectively). The XRD patterns of fresh catalysts indicated the formation of well-crystallized perovskite structure as the main phase present in the prepared samples. The results showed that the highly homogeneous and pure solids with particle sizes in the range of nanometers were obtained through this synthesis method. TPR analysis revealed that by increasing the degree of substitution (x) the reduction of the prepared samples became difficult. The effects of the partial substitution of Ni by Fe and reaction temperatures at atmospheric pressure were investigated in the combined reforming of methane with CO₂ and O₂ (CRM), after reduction of the samples under hydrogen. LaNiO₃ exhibited high activity and selectivity without coke formation between all of the studied perovskites. Among Fe-substituted catalysts, the following order of activity was observed: LaNiO₃>LaNi_0.4Fe_0.6O₃>LaNi_0.6Fe_0.4O₃ > LaNi_0.8Fe_0.2O₃ > LaNi_0.2Fe_0.8O₃ > LaFeO₃.     

A numerical study on the effects of H2 addition in non-premixed turbulent combustion of C3H8–H2–N2 mixture using a steady flamelet approach

This study has been implemented in two sections. At first, the turbulent jet flame of DLR-B is simulated by combining the k–ε turbulence model and a steady flamelet approach. The DLR-B flame under consideration has been experimentally investigated by Meier et al. who obtained velocity and scalar statistics. The fuel jet composition is 33.2% H₂, 22.1% CH₄ and 44.7% N₂ by volume. The jet exit velocity is 63.2 m/s resulting in a Reynolds number of 22,800. Our focus in the first part is to validate the developed numerical code. Comparison with experiments showed good agreement for temperature and species distribution. At the second part, we exchanged methane with propane in the fuel composition whilst maintaining all other operating conditions unchanged. We investigated the effect of hydrogen concentration on C₃H₈–H₂–N₂ mixtures so that propane mole fraction extent is fixed. The hydrogen volume concentration rose from 33.2% up to 73.2%. The achieved consequences revealed that hydrogen addition produces elongated flame with increased levels of radiative heat flux and CO pollutant emission. The latter behavior might be due to quenching of CO oxidation process in the light of excessive cold air downstream of reaction zone.     

Numerical simulations of non-premixed turbulent combustion of CH4–H2 mixtures using the PDF approach

The present work is devoted to the study of non-premixed turbulent combustion with the PDF approach using three turbulence models: k-? model, modified k-? model and RSM model. A detailed kinetic mechanism is used in the numerical simulations. The three turbulence models are compared and evaluated with the experimental data and the numerical results of the literature. The evaluation concludes that the modified k-? is the most appropriate for simulating this kind of flame. A study of the effect of hydrogen addition on methane combustion is performed. Hydrogen addition causes the elevation of combustion temperature, the decreasing of CO and CO₂ mass fractions but leads to the increase of NO mass fraction.     

Effect of CO and CO2 on H2 permeation through finger-like Pd–Ag membranes

The permeance of a 50 μm thick PdAg (25 wt.% of silver) tubular membrane towards hydrogen was evaluated for hydrogen feed streams or binary mixtures of industrial relevance, namely of H₂/CO or H₂/CO₂.