Kinetic incentive of hydrogen addition on nonpremixed laminar methane/air flames

In order to find out the respective influences of chemical reactivity and physical transport of hydrogen additive on nonpremixed flame, two fabricated hydrogen additions were introduced into nonpremixed methane/air flame modeling. Hydrogen addition was assumed as inert gas or partial reactivity fuel to respectively explore the kinetic reasons by the three aspects: the elementary reaction route, heat release, and physical diffusion of hydrogen addition. The analyses were implemented in terms of OH and H production. Results showed that, hydrogen addition can enhance OH and H production via elementary reactions, and causes flame reaction zone migration through the coupling interaction between the low-temperature heat enthalpy release and diffusion behavior of hydrogen addition. R84 (OH + H₂=H + H₂O) and R38 (H + O₂=O + OH) are the most important elementary reactions related to OH and H production. The physical incentive of hydrogen addition can hardly work without the chemical effects of hydrogen addition.     

Numerical study of the physical and chemical effects of hydrogen addition on laminar premixed combustion characteristics of methane and ethane

Methane and ethane are taken as the research objects. Using H₂ as diluent, based on Chemkin II/Premix Code and modified detailed chemical reaction mechanism: GRI 3.0*-Mech (introducing three hypothetical substances of FH₂, FO₂ and FN₂), the physical and chemical effects of hydrogen on laminar burning velocities (LBVs), adiabatic flame temperatures (AFTs), net heat release rates (NHRRs) and elementary reactions responsible for temperature changes of two alkanes under different equivalence ratios were analyzed and determined. Results showed that the chemical effect of H₂ promotes the LBVs and ATFs of methane and ethane, while the physical effect decreases the two parameters. In addition, the physical effects of H₂ inhibit the chemical reactions of methane and ethane, resulting in the decrease of NHRRs. The chemical effect of H₂ accelerates the process of chemical reaction and obviously increases the NHRRs. The two most vital elementary reactions that promote the temperature rise of methane and ethane are H + O₂ <=> OH + O and CO + OH <=> H + CO₂. The important reactions responsible for inhibiting the temperature rise are H + CH₃(+M) <=> CH₄(+M) and H + O₂ + H₂O <=> HO₂ + H₂O.     

A computational study of combustion and extinction of opposed-jet syngas diffusion flames

This paper reports a numerical study on the combustion and extinction characteristics of opposed-jet syngas diffusion flames. A model of one-dimensional counterflow syngas diffusion flames was constructed with constant strain rate formulations, which used detailed chemical kinetics and thermal and transport properties with flame radiation calculated by statistic narrowband radiation model. Detailed flame structures, species production rates and net reaction rates of key chemical reaction steps were analyzed. The effects of syngas compositions, dilution gases and pressures on the flame structures and extinction limits of H₂/CO synthetic mixture flames were discussed. Results indicate the flame structures and flame extinction are impacted by the compositions of syngas mixture significantly. From H₂-enriched syngas to CO-enriched syngas fuels, the dominant chain reactions are shifting from OH + H₂→H + H₂O for H₂O production to OH + CO→H + CO₂ for CO₂ production through the key chain-branching reaction of H + O₂→O + OH. Flame temperature increases with increasing hydrogen content and pressure, but the flame thickness is decreased with pressure. Besides, the study of the dilution effects from CO₂, N₂, and H₂O, showed the maximum flame temperature is decreased the most with CO₂ as the dilution gas, while CO-enriched syngas flames with H₂O dilution has highest maximum flame temperature when extinction occurs due to the competitions of chemical effect and radiation effect. Finally, extinction limits were obtained with minimum hydrogen percentage as the index at different pressures, which provides a fundamental understanding of syngas combustion and applications.     

Experimental and numerical study on the laminar burning velocity of hydrogen enriched biogas mixture

The laminar burning velocities of biogas-hydrogen-air mixture at different fuel compositions and equivalence ratios were determined and studied using the spherical flame method. The combined effects of H₂ and CO₂ on the laminar burning velocity were investigated quantitatively based on the kinetic effects and the thermal effects. The results show that the laminar burning velocities of the BG40, BG50 and BG60 are increased almost linearly with the H₂ addition owing to the improved fuel kinetics and the increased adiabatic flame temperature. The dropping trend of laminar burning velocity from the BG60-hydrogen to the BG40-hydrogen is primarily attributed to the decreased adiabatic flame temperature (thermal effects). The GRI 3.0 mechanism can predict the laminar burning velocity of biogas-hydrogen mixture better than the San Diego mechanism in this study. Whereas, the GRI mechanism still needs to be modified properly for the hydrogen-enriched biogas as the CO₂ proportion exceeds 50% in the biogas at the fuel-rich condition. The increased CO₂ exerts the stronger suppression on the net reaction rate of H + O₂=OH + O than that of H + CH₃(+M) = CH₄(+M), which contributes to that the rich-shift of peak laminar burning velocity of biogas-hydrogen mixture requires higher H₂ addition as the CO₂ content is enhanced. For the biogas-hydrogen fuel, the H₂ addition decreases the flame stability of biogas fuel effectively due to the increased diffusive-thermal instability and hydrodynamic instability. The improved flame stability of biogas-hydrogen fuel with the increased CO₂ content is resulted from the combined effects of diffusive-thermal instability and hydrodynamic instability.     

Numerical investigation on the effect of CO2 and steam for the H2 intermediate formation and NOX emission in laminar premixed methane/air flames

One-dimensional premixed freely-propagating flames for (CH₄+CO₂/H₂O)/air(79%N₂+21%O₂) mixtures were modeled using ChemkinⅡ/Premix Code with the detailed mechanism GRI-Mech 3.0. The investigation of the effects of CO₂ and steam addition on the H₂ intermediate formation and NO emission was conducted at the initial conditions of 1 atm and 398 K. Both physical and chemical effects of CO₂, H₂O on laminar burning velocities and adiabatic flame temperatures were also analyzed. The calculations show that with the increase of α_CO2 and α_H2O, both physical and chemical effects of CO₂ and H₂O result in the reduction of laminar burning velocities (LBVs) and adiabatic flame temperatures (AFTs) in which the chemical effects of CO₂ addition are more significantly than H₂O. Especially, the chemical effects of steam promote the increase of AFTs and the influence in rich BG65 flames are larger than in methane. With a proper amount of H₂O addition, the chemical effects of H₂O on the peak concentration of H₂ are more significantly than physical at Φ = 1.2. Moreover, CO₂, steam and their mixture addition have significant reduction on the NO emission. The most sensitive reaction for the formation of H₂ and NO emission were determined. The responsible reactions for H₂ formation and NO emission are R84 OH + H₂ <=> H + H₂O and R240 CH + N₂ <=> HCN + N (a prompt routine), respectively.     

Comparative study on the effect of CO2 and H2O dilution on laminar burning characteristics of CO/H2/air mixtures

A study on the effect of CO₂ and H₂O dilution on the laminar burning characteristics of CO/H₂/air mixtures was conducted at elevated pressures using spherically expanding flames and CHEMKIN package. Experimental conditions for the CO₂ and H₂O diluted CO/H₂/air/mixtures of hydrogen fraction in syngas from 0.2 to 0.8 are the pressures from 0.1 to 0.3 MPa, initial temperature of 373 K, with CO₂ or H₂O dilution ratios from 0 to 0.15. Laminar burning velocities of the CO₂ and H₂O diluted CO/H₂/air/mixtures were measured and calculated using the mechanism of Davis et al. and the mechanism of Li et al. Results show that the discrepancy exists between the measured values and the simulated ones using both Davis and Li mechanisms. The discrepancy shows different trends under CO₂ and H₂O dilution. Chemical kinetics analysis indicates that the elementary reaction corresponding to peak ROP of OH consumption for mixtures with CO/H₂ ratio of 20/80 changes from reaction R3 (OH + H₂ = H + H₂O) to R16 (HO₂+H = OH + OH) when CO₂ and H₂O are added. Sensitivity analysis was conducted to find out the dominant reaction when CO₂ and H₂O are added. Laminar burning velocities and kinetics analysis indicate that CO₂ has a stronger chemical effect than H₂O. The intrinsic flame instability is promoted at atmospheric pressure and is suppressed at elevated pressure for the CO₂ and H₂O diluted mixtures. This phenomenon was interpreted with the parameters of the effective Lewis number, thermal expansion ratio, flame thickness and linear theory.     

Detailed kinetic modeling of homogeneous HI decomposition for hydrogen production,part I: Effect of H2O on HI decomposition

A new, detailed kinetic model was developed for the homogeneous decomposition of HI–H₂O solutions in vapor phase in the sulfur–iodine cycle. The kinetics of the process was represented by a reaction mechanism involving 32 reactions and 11 species. Comparisons between the kinetic calculations and experimental data showed that this model correctly predicted the hydrogen yield at the 500 °C–1000 °C temperature range under 1 atm. The effects of temperature, reaction time, and HI/H₂O ratio on HI decomposition and hydrogen sensitivity analysis were investigated in the modeling process. The model predicted that the effect of the addition of H₂O changed from inhibiting the decomposition ratio to promoting it with increasing temperature. The sensitivity analysis showed that elementary reactions (1) HI + HI = H₂+I₂, (4) HI + H = H₂ + I, (5) HI + I = H + I₂, and (8) HI + OH = H₂O + I played important roles in hydrogen production. The reaction path of HI decomposition with H₂O was constructed based on detailed kinetic modeling and sensitivity analysis results.     

Effects of CO addition on laminar flame characteristics and chemical reactions of H2 and CH4 in oxy-fuel (O2/CO2) atmosphere

An experimental study is conducted to investigate the effect of CO addition on the laminar flame characteristics of H₂ and CH₄ flames in a constant-volume combustion system. In addition, one-dimensional laminar premixed flame propagation processes at the same conditions are simulated with the update mechanisms. Results show that all mechanisms could well predict the laminar flame speeds of CH₄/CO/O₂/CO₂ mixtures, when Z_CO is large. For mixtures with lower CO, the experimental laminar flame speeds are always smaller than the calculated ones with Han mechanism. For mixtures with larger or smaller Z_CO2, GRI 3.0, San diego and USC 2.0 mechanisms all overvalue or undervalue the laminar flame speeds. When CO ratio in the CH₄/CO blended fuels increases, laminar flame speed firstly increases and then decreases for the CH₄/CO/O₂/CO₂ mixtures. For H₂/CO/O₂/CO₂ mixtures, San diego, Davis and Li mechanisms all undervalue the laminar flame speeds of H₂/CO/CO₂/CO₂ mixtures. Existing models could not well predict the nonlinear trend of the laminar flame speeds, due to complex chemical effects of CO on CH₄/CO or H₂/CO flames. Then, the detailed thermal, kinetic and diffusive effects of CO addition on the laminar flame speeds are discussed. Kinetic sensitivity coefficient is far larger than thermal and diffusive ones and this indicates CO addition influences laminar flame speeds mainly by the kinetic effect. Based on this, radical pool and sensitivity analysis are conducted for CH₄/CO/O₂/CO₂ and H₂/CO/O₂/CO₂ mixtures. For CH₄/CO/O₂/CO₂ mixtures, elementary reaction R38H + O₂ ↔ O + OH and R99 OH + CO ↔ H + CO₂ are the most important branching reactions with positive sensitivity coefficients when CO ratio is relative low. As CO content increases in the CH₄/CO blended fuel, the oxidation of CO plays a more and more important role. When CO ratio is larger than 0.9, the importance of R99 OH + CO ↔ H + CO₂ is far larger than that of R38H + O₂ ↔ O + OH. The oxidation of CO dominates the combustion process of CH₄/CO/O₂/CO₂ mixtures. For H₂/CO/O₂/CO₂ mixtures, the most important elementary reaction with positive and negative sensitivity coefficients are R29 CO + OH ↔ CO₂ + H and R13H + O₂(+M) ↔ HO₂(+M) respectively. The sensitivity coefficient of R29 CO + OH ↔ CO₂ + H is increasing and then decreasing with the addition of CO in the mixture. Chemical kinetic analysis shows that the chemical effect of CO on the laminar flame propagation of CH₄/CO/O₂/CO₂ and H₂/CO/O₂/CO₂ mixtures could be divided into two stages and the critical CO mole fraction is 0.9.     

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.     

Extinction studies of near-limit lean premixed syngas/air flames

Extinction studies of weakly-stretched near-limit lean premixed syngas/air flames were conducted in a twin-flame counterflow configuration. Experiments showed that buoyancy-induced natural convection at normal gravity strongly disturbed these flames. In order to validate the simulation, accurate extinction data was obtained at micro-gravity. Experimental data obtained from the 3.6 s micro-gravity drop tower showed that the extinction equivalence ratio increased with the increasing global stretch rate and decreased with the increasing H₂ mole fraction in the fuel. Numerical simulation was conducted with CHEMKIN software using GRI 3.0 and USC-Mech II mechanisms. The predicted extinction limit trend was in agreement with the micro-gravity experimental data. Sensitivity analyses showed that the competition between the main branching reaction H + O₂ ⇔ O + OH and the main termination reaction H + O₂ + M ⇔ HO₂ + M in the H₂/O₂ chemistry determined the extinction limits of the flames. The dominant species for syngas/air flame extinction was the H radical. The key exothermal reaction changed from OH + CO ⇔ H + CO₂ to OH + H₂ ⇔ H + H₂O with the increasing H₂ mole fraction in the fuel. Also, the mass diffusion played a more important role than chemical kinetics in the flame extinction. When the H₂ mass diffusion was suppressed, the reaction zone was pushed to the stagnation plane and the flame became weaker; while H mass diffusion is suppressed, the reaction zone slightly shifted towards the upstream and the flame was slightly strengthened.