Effects of nitrogen and argon on ammonia-oxygen explosion

The primary task of this work is to clarify ammonia-oxygen explosion characteristics under nitrogen and argon atmosphere. Firstly, the flame behavior and explosion pressure are experimentally obtained. Then their correlation is revealed quantitatively. The thermal, diffusive and chemical analysis is conducted at last. The results demonstrated that the variation tendency of flame propagation velocity (FPV), maximum explosion pressure (MEP) and maximum rate of pressure rise (MRPR) is completely consistent. All index of FPV, MEP and MRPR, becomes increased and decreased with increasing equivalence ratio, continues to decrease with increasing inert gas fraction. All index of FPV, MEP and MRPR under argon atmosphere is totally larger than that under nitrogen atmosphere. By considering the state equation of ideal gas, spherically smooth flame and adiabatic compression, the flame behavior and explosion pressure under nitrogen and argon atmosphere is significantly controlled by laminar burning speed (LBS). As the inert gas fraction and equivalence ratio change, the LBS under nitrogen and argon atmosphere is significantly controlled by adiabatic flame temperature. The joint action of adiabatic flame temperature and thermal diffusivity contributes to the LBS difference.     

Dynamic couplings of hydrogen/air flame morphology and explosion pressure evolution in the spherical chamber

This paper aims at exploring the dynamic couplings of flame morphology and explosion pressure evolution experimentally and theoretically. In the experiment, flame morphology and explosion pressure evolution under diffusional-thermal and hydrodynamic instability are recorded using high-speed schlieren photography and pressure transducer. In the theoretical calculation, the effects of cellular flame on the explosion pressure evolution are conducted using smooth flame, D = 2.0566, 2.1 and 7/3. The results demonstrate that the cellular flame formation of various equivalence ratios could be attributed to the fact Lewis number is less than unity on the lean side. The flame destabilization of Φ = 0.8 and 3.0 with increasing initial pressure is due to the decreasing flame thickness regardless of unchangeable thermal expansion ratio. Much smaller cells formation on the cellular flame surface as the explosion pressure rises could be attributed to the joint effect of the diffusional-thermal and hydrodynamic instability. Note that the explosion pressure evolution in spherical chamber is obviously underestimated assuming the flame surface is smooth during the hydrogen/air explosion. But the explosion overpressure is overpredicted significantly with D = 7/3. The theoretical overpressure with D = 2.1 is in satisfactory agreement with experimental results.     

On the explosion limit of syngas with CO2 and H2O additions

In this study, the pressure-temperature explosion limits of H₂/CO/O₂/CO₂/H₂O mixtures are analyzed computationally and theoretically. The result indicates that with the increase of H₂O and CO₂ mole fractions, the explosion temperatures are increased around all the three explosion limits. Furthermore, the increase of the explosion temperature is higher with the addition of H₂O compared with the addition of CO₂ near the second explosion limit. In addition, the increase of the explosion temperature near the first and third explosion limit is almost the same for the addition of these two inter gases. The single-limit expression analysis shows that the first explosion limit is mainly controlled by the changing of the oxygen concentration with the addition of inert gas; the changing of the second explosion limit is caused by the changing of the reaction rate of H + O₂ (+M)→HO₂ (+M), which is indirectly through the Chaperon efficiency of the third body recombination reaction, and the effect of inert gas addition on the third explosion limit is mainly caused by the changing of the hydrogen concentration.     

Effects of diluents on the ignition of premixed H2/air mixtures

A computational study is performed to investigate the effects of diluents on the ignition of premixed H₂/air mixtures. The ignition processes for fuel lean, stoichiometric, and fuel rich H₂/air mixed with different diluents (He, Ar, N₂, and CO₂) are simulated with detailed chemistry and variable thermodynamic and transport properties. The minimum ignition energies (MIE) for different diluents at different dilution ratios are obtained. It is found that the change of the MIE with the dilution ratio consists of two regimes: in the first regime with a small value of dilution ratio, diluent addition has little effect on the MIE and in the second regime with dilution ratio above a certain value, the MIE increases exponentially with the dilution ratio. The kinetic and radiation effects of dilution are assessed by conducting sensitivity analysis and using the optically thin model, respectively. The thermal and flame-dynamic effects of dilution, characterized by the adiabatic flame temperature and Markstein length, respectively, are also discussed. Moreover, the dilution limits for H₂/air mixtures at different equivalence ratios are obtained. The dilution limits predicted by present ignition calculation are found to agree well with those based on laminar flame speed measurements at micro-gravity conditions. The ranking in terms of the effectiveness on ignition inhibition for stoichiometric H₂/air is shown to be in the order of Ar, N₂, He, and CO₂. The dilution limit is of practical interest since it is a measure of the efficiency of the diluent in fire prevention and suppression.     

惰性颗粒抑制CH4/O2/N2爆炸过程的二维数值模拟与实验验证

使用带基元化学反应的两相Euler方程,对惰性颗粒抑制高温火团诱导的CH4/O2/N2爆炸过程进行了二维数值模拟.其中,采用全耦合二阶精度的TVD格式求解气相方程,采用MacCormack格式求解惰性颗粒相方程,同时用分步方法处理方程组的耦合刚性,用Gear隐式方法处理化学反应刚性.计算并讨论了不同颗粒相浓度条件下,气相压力场、气相密度和颗粒相浓度的分布、爆炸衰减的气相结构以及两相间的能量传递.结果表明,惰性颗粒相的堆积可阻碍气相爆炸波的传播,使其衰减为引导激波,引导激波继续向颗粒相传递能量,而进一步衰减最终使得爆炸波被抑制.随着颗粒相浓度的增大,爆炸波的抑制更明显.计算结果与大型水平管的实验结果进行了比较,定性证明了计算的合理性.     

Thermal desorption processes of H2 and CH4 from Li2ZrO3 and Li4SiO4 materials absorbed H2O and CO2 in air at room temperature

The thermal desorption processes of hydrogen (H₂) and methane (CH₄) from lithium-based materials, Li₂ZrO₃ and Li₄SiO₄, exposed to air at room temperature of 293 K with a relative humidity of 80%, were investigated using gas chromatography (GC). The GC analysis revealed that the absolute values of the released H₂ and CH₄ gases at 523 K were approximately 7.42 × 10^?6 and 1.54 × 10^?6 ml/g for Li₂ZrO₃, and 3.24 × 10^?6 and 0 ml/g for Li₄SiO₄. The amounts of H₂ and CH₄ released increased with increase in annealing temperatures and considerably depended on absorption properties of water (H₂O) and carbon dioxide (CO₂) present in air at room temperature. The production of CH₄ at low temperature is due to the intermediate species including CH_x precursors produced by the reaction between H split from H₂O and Li₂CO₃ resulting in the CO₂ absorption of Li₂ZrO₃ and Li₄SiO₄ materials.     

Numerical and experimental study of the influence of CO2 dilution on burning characteristics of syngas/air flame

In this study, effect of carbon dioxide dilution on explosive behavior of syngas/air mixture was investigated numerically and experimentally. Explosion in a 3-D cylindrical geometry model with dimensions identical to the chamber used in the experiment was simulated using ANSYS Fluent. The simulated results showed that after ignition, the flame front propagated outward spherically until it touched the wall, like the propagating flame observed in the experiment. Both experimental and simulated results presented a same trend of decreasing the maximum explosion pressure and prolonging the explosion time with CO₂ dilution. The results showed that for CO₂ additions, the maximum explosion pressure decreased linearly and the explosion time increased linearly, while the maximum rate of pressure rise decreased nonlinearly, which can be correlated to an exponential equation. In addition, both results showed a good agreement for syngas/air flame with CO₂ addition up to 20% in volume. However, larger discrepancies were observed for higher levels of CO₂ dilutions. Of the three diluents tested, carbon dioxide displayed the strongest effect in reducing explosion hazard of syngas/air flame compared to helium and nitrogen. Chemical kinetic analysis results showed that maximum concentration of major radicals and net reaction rates of important reactions drastically decreased with CO₂ addition, causing a reduction of laminar flame speed.     

Direct numerical simulation of lean premixed CH4/air and H2/air flames at high Karlovitz numbers

Three-dimensional direct numerical simulation with detailed chemical kinetics of lean premixed CH₄/air and H₂/air flames at high Karlovitz numbers (Ka ∼ 1800) is carried out. It is found that the high intensity turbulence along with differential diffusion result in a much more rapid transport of H radicals from the reaction zone to the low temperature unburned mixtures (∼500 K) than that in laminar flamelets. The enhanced concentration of H radicals in the low temperature zone drastically increases the reaction rates of exothermic chain terminating reactions (e.g., H + O₂+M = HO₂ + M in lean H₂/air flames), which results in a significantly enhanced heat release rate at low temperatures. This effect is observed in both CH₄/air and H₂/air flames and locally, the heat release rate in the low temperature zone can exceed the peak heat release rate of a laminar flamelet. The effects of chemical kinetics and transport properties on the H₂/air flame are investigated, from which it is concluded that the enhanced heat release rate in the low temperature zone is a convection–diffusion-reaction phenomenon, and to obtain it, detailed chemistry is essential and detailed transport is important.     

Assessment of the method for calculating the Lewis number of H2/CO/CH4 mixtures and comparison with experimental results

This paper investigates the various techniques used in the literature to calculate the effective Lewis number of two-component (H₂/CO and H₂/CH₄) and three-component fuels (H₂/CO/CH₄ and H₂/CO/CO₂) over a wide range of equivalence ratios (0.6 ≤ φ ≤ 1.4) under laminar flame conditions. The most appropriate effective Lewis number formulation is identified through comparison with experimentally extracted Lewis numbers (Le). The paper first identifies the proper methodology to extract the experimental Le from the burned Markstein length of an outwardly propagating flame. Second, the different methodologies for the calculation of the effective Le are presented and compared to experimental results for H₂/CH₄ and H₂/CO mixtures. Based on the experimental results, it is shown that the calculation of the effective Le of mixtures can be divided into a three-step procedure depending on the equivalence ratio: (1) calculation of the Le for each fuel and the oxidizer; (2) use of the Le mixing rule; and (3) assessment of the necessity or not of combining the fuel's and oxidizer's Lewis numbers. The paper shows that, in rich mixtures, the oxidizer Le needs to be taken into account. Lastly, the methodology is validated for H₂/CO/CH₄ and H₂/CO/CO₂ fuels.     

Effect of high hydrogen enrichment on the outer-shear-layer flame of confined lean premixed CH4/H2/air swirl flames

In this study, we investigated the H₂-induced transition of confined swirl flames from the “V” to “M” shape. H₂-enriched lean premixed CH₄/H₂/air flames with H₂ fractions up to 80% were conducted. The flame structure was obtained with Planar Laser-Induced Fluorescence (PLIF) of the OH radical. Flow fields were measured with Particle Image Velocimetry (PIV). It was observed that the flame tip in the outer shear layer gradually propagated upstream and finally anchored to the injector with the hydrogen fractions increase, yielding the transition from the “V” to “M” flame. We examined the flame structures and the flame flow dynamics during the transition. The shape transition was directly related to the evolution of the corner flame along the outer shear layer. With H₂ addition, the outer recirculation zone first appeared downstream where the corner flame started to propagate upstream; then, the recirculation zone expanded upward to form a stable “M” flame gradually. The flow straining was observed to influence the stabilization of the outer shear layer flame significantly. This study can be useful for the understanding of recirculation-stabilized swirling flames with strong confinement. The flame structure and the flow characteristics of flames with a high H₂ content are also valuable for model validation.     

Effects of steam dilution on laminar flame speeds of H2/air/H2O mixtures at atmospheric and elevated pressures

The laminar flame speeds of H₂/air with steam dilution (up to 33 vol%) were measured over a wide range of equivalence ratio (0.9–3.0) at atmospheric and elevated pressures (up to 5 atm) by an improved Bunsen burner method. Burke, Sun, HP (High Pressure H₂/O₂ mechanism), and Davis mechanisms were employed to calculate the laminar flame speeds and analyze different effects of steam addition. Four studied mechanisms all underestimated the laminar flame speeds of H₂/air/H₂O mixtures at medium equivalence ratios while the Burke mechanism provided the best estimates. When the steam concentration was lower than 12%, increasing pressure first increased and then decreased the laminar flame speed, the inflection point appeared at 2.5 atm. When the steam concentration was greater than 12%, increasing the pressure monotonously decrease the laminar flame speed. The chemical effect was amplified by elevated pressure and it played an important role for the inhibiting effect of the pressure on laminar flame speed. The fluctuations of the chemical effect at 1 atm were mainly caused by three-body reactions, while the turn at 5 atm was mainly caused by the direct reaction effect. Elevated pressure and steam addition amplified the influences of uncertainties in the rate constants for elementary reactions, which might leaded to the disagreement between experimental and simulation results.     

铝锂/镁合金与H_2O反应的热力学分析

根据吉布斯能最小原理,利用FactSage计算研究了Al-Li-H2O体系和Al-Mg-H2O反应体系的热力参数,研究了温度、合金组成和H2O量的影响。结果表明:Al-Li-H2O体系氧化反应可以自发进行,随着温度的升高反应放出的热量减少;合金组成中Al含量越高,生成的H2越少;随着Li含量增大,固态产物由Al2O3向LiAlO2、Li2O转变。Al-Mg-H2O体系氧化反应可以自发进行,随着温度的升高反应放出的热量减少;合金组成中Al含量越高生成的H2越多;随着Mg含量增大,最终固态产物由Al2O3向MgAl2O4、MgO转变。Al中添加Li或Mg因产物发生转变而对制氢反应有促进作用;H2O量增加有助于反应最终温度的降低,温差为1800~2000 K,对金属制氢的实施应用有指导意义。     

Enhancing energy storage efficiency of lithiated carbon nitride (C7N6) monolayers under co-adsorption of H2 and CH4

There is a great interest in the design of innovative concepts and strategies of nitrogen rich carboneous materials for exploring their hydrogen (H₂) storage properties. Methane (CH₄) storage can be an alternative to H₂ because the combustion energy of the former is around three times higher than the latter. However, strong inter-molecular repulsion between the CH₄ molecules is a major bottleneck to achieve a high gravimetric density. In this study, we use first principles density functional calculations to investigate the coadoption of H₂ and CH₄ on Li decorated carbon nitride (Li–C₇N₆) monolayer. The repulsion between CH₄ molecules has been avoided by keeping them in asymmetric configuration whereas the repulsion between CH₄–H₂ is in moderation due to the exploitation of open Li doped sites on C₇N₆ surface. Though Li–C₇N₆ has a lower H₂ or CH₄ storage capacity due to weak van der Waals interactions, the capacity could be doubled with a novel strategy of co-mixing of H₂ with CH₄ which results into a significantly high gravimetric density of 8.1 wt%. This clearly shows that the CH₄–H₂ co-mixing strategies have the potential to further propel the prospects of C₇N₆ monolayers for reversible clean energy storage applications.     

Calculation of CO2, CH4 and H2S solubilities in aqueous electrolyte solution at high pressure and high temperature

This paper reports an investigation into the characterisation of liquid-vapor electrolyte solutions at high pressure and high temperature,A procedure to enable calculations of methane,carbon dioxide and hydrogen sulphide solubilities in brines(0-6m.) for temperature from 25 to 350℃ and for pressures from 1 to 1800 bar is presented.The model is based on Helgeson,Kirkham and Flowers modified equations of state(HKF)and on the semi-empirical interaction model introduced by Pitzer,HKF modified equations of state are used to calculate the reference fugacity of gas species,and the Pitzer ionic interaction model is used to calculate the activity coefficient of dissolved species(i.e.ionic or neutral).The efficiency of the combination of the two models is confirmed by several comparisons with data in the literature.     

Effects of fluorine-substitution on the electrochemical behavior of LiFePO4/C cathode materials

The effects of fluorine substitution on the electrochemical properties of LiFePO₄/C cathode materials were studied. Samples with stoichiometric proportion of LiFe(PO₄)_1−xF_3x/C (x = 0.025, 0.05, 0.1) were prepared by adding LiF in the starting materials of LiFePO₄/C. XRD and XPS analyses indicate that LiF was completely introduced into bulk LiFePO₄ structure in LiFe(PO₄)_1−xF_3x/C (x = 0.025, 0.05) samples, while there was still some excess of LiF in LiFe(PO₄)_0.9F_0.3/C sample. The results of electrochemical measurement show that F-substitution can improve the rate capability of these cathode materials. The LiFe(PO₄)_0.9F_0.3/C sample showed the best high rate performance. Its discharge capacity at 10 C rate was 110 mAh g⁻¹ with a discharge voltage plateau of 3.31–3.0 V versus Li/Li⁺. The LiFe(PO₄)_0.9F_0.3/C sample also showed obviously better cycling life at high temperature than the other samples.     

Effects of density ratio and differential diffusion on flame accelerative propagation of H2/O2/N2 mixtures

The effects of density ratio and differential diffusion on premixed flame propagation of H₂/O₂/N₂ mixtures are investigated by constant volume combustion chamber. The density ratio and differential diffusion are controlled independently by adjusting the O₂/N₂ ratio and equivalence ratio. Results show that the density ratio has no effect on turbulent burning velocity while the differential diffusion has a promotion effect on turbulent burning velocity. The onsets of laminar flame acceleration are promoted by both density ratio and differential ratio. The turbulent flames perform a continuous acceleration propagation and the dependence between flame propagation speed and flame radius can be characterized as (dR/dt)/(σ·S_L) ～ R^0.33～0.37, which is lower than the 1/2 power law. The acceleration parameters of laminar flames and turbulent flames (u^’/S_L = 1) are around 0.17 and 0.36 respectively, and both of them are not affected by density ratio and differential diffusion. The empirical formula m = 0.19·(u^’/S_L)^0.4+0.17 is concluded to quantitatively describe the accelerative characteristics of laminar and turbulent flames. The current study indicates that the acceleration of laminar flames is mainly induced by flame intrinsic instability, and the latter can affect the acceleration onset but not affect the fractal excess. The acceleration of turbulent flames is dominated by turbulent stretch, while the effects of density ratio and differential diffusion can be ignored.     

Effects of annealing temperature on the structure and properties of the LaY2Ni10Mn0.5 hydrogen storage alloy

The effects of annealing at 1123, 1148, 1173 and 1198 K for 16 h on the structure and properties of the LaY₂Ni₁₀Mn_0.5 hydrogen storage alloy as the active material of the negative electrode in nickel–metal hydride (Ni–MH) batteries were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy linked with an energy dispersive X-ray spectrometer (SEM–EDS), pressure-composition isotherms (PCI) and electrochemical measurements. The quenched and annealed LaY₂Ni₁₀Mn_0.5 alloys primarily consist of Ce₂Ni₇- (2H) and Gd₂Co₇-type (3R) phases. The homogeneity of the composition and plateau characteristics of the annealed alloys are significantly improved, and the lattice strain is effectively reduced. The alloys annealed at 1148 K and 1173 K have distinctly greater hydrogen storage amounts, 1.49 wt% (corresponding to 399 mAh g^?1 in equivalent electrochemical units) and 1.48 wt%, respectively, than the quenched alloy (1.25 wt%, corresponding to 335 mAh g^?1 in equivalent electrochemical units). The alloys annealed at 1148 K and 1173 K have relatively good activation capabilities. The annealing treatment slightly decreases the discharge potentials of the alloy electrodes but markedly increases their discharge capacity. The maximum discharge capacities of the annealed alloy electrodes (372–391 mAh g^?1) are greater than the extreme capacity of the LaNi₅-type alloy (370 mAh g^?1). The cycling stability of the annealed alloy electrodes was improved.     

Effects of hydrogen on the interfacial reaction between Ti6Al4V alloy melt and Al2O3 ceramic shell

Effects of hydrogen on the interfacial reaction between Ti6Al4V (Ti64) alloy melt and Al₂O₃ ceramic shell were studied by arc-melting in H₂/Ar gaseous mixture. The thickness of interfacial reaction layer between Ti64 alloy melt and Al₂O₃ ceramic shell without hydrogenation is 80 μm. But the thickness of reaction layer can be reduced to 10 μm at a hydrogen partial pressure of 20 kPa, which is better than the thickness of interface layer between Ti64 alloy and widely used Y₂O₃ shells. At Ti64 casting surface, the content of β-soft ductile phase is increased and the width of both reaction zone and transition zone are reduced with the increase of hydrogen partial pressure, thus reduces the hardness and the element diffusion distance. Therefore, Hydrogen can effectively control the interfacial reaction in the process of titanium alloy investment casting, and Al₂O₃ ceramic will be a kind of very promising shell material.     

Effects of Pt/C, Pd/C and PdPt/C anode catalysts on the performance and stability of air breathing direct formic acid fuel cells

Pt/C, Pd/C and PdPt/C catalysts are potential anodic candidates for electro-oxidation of formic acid. In this work we designed a miniature air breathing direct formic acid fuel cell, in which gold plated printed circuit boards are used as end plates and current collectors, and evaluated the effects of anode catalysts on open circuit voltage, power density and long-term discharging stability of the cell. It was found that the cell performance was strongly anode catalyst dependent. Pd/C demonstrated good catalytic activity but poor stability. A maximum power density of 25.1 mW cm⁻² was achieved when 5.0 M HCOOH was fed as electrolyte. Pt/C and PdPt/C showed poor activity but good stability, and the cell can discharge for about 10 h at 0.45 V (Pt/C anode) and 15 h at 0.3 V (PdPt/C) at 20 mA.     

膜分离法、化学吸收法以及联合法分离CO_2/CH_4试验比较

在中空纤维膜和化学吸收塔的试验台上,分别采用膜分离法、化学吸收法进行了CO2/CH4混合气体的分离试验.在此基础上提出了联合法新型CO2脱除技术,并在中空纤维膜串联化学吸收塔的试验台上进行了CO2/CH4混合气体分离试验,重点考察了各影响因素对各分离方法脱碳效果的影响,并对各分离方法脱碳效果进行了对比.结果表明:膜分离法的脱碳效率低且CH4损失率高,适用于处理小流量且对脱碳效率要求不高的工艺;化学吸收法的脱碳效率和CH4回收率高,适用于分离纯度要求高的工艺;联合法脱碳效率偏低但CH4损失率低,适用于处理大流量且对脱碳效率要求不高的工艺.