Laminar burning velocities and flame stability analysis of H2/CO/air mixtures with dilution of N2 and CO2

Experimental measurement of the laminar burning velocities of H₂/CO/air mixtures and equimolar H₂/CO mixtures diluted with N₂ and CO₂ up to 60% and 20% by volume, respectively, were conducted at different equivalence ratios and conditions near to the sea level, 0.95 atm and 303 ± 2 K. Flames were generated using contoured slot-type nozzle burners and Schlieren images were used to determine the laminar burning velocity with the angle method. Numerical calculations were also conducted using the most recent detailed reaction mechanisms for comparison with the present experimental results. Additionally, a study was conducted to analyze the flame stability phenomenology that was found in the present experiments. The increase in the N₂ and CO₂ dilution fractions considerably reduced the laminar burning velocity due to the decrease in heat release and increase in heat capacity. At the same dilution fractions this effect was higher for the case of CO₂ due to its higher heat capacity and dissociation effects during combustion. Flame instabilities were observed at lean conditions. While the presence of CO in the fuel mixture tends to stabilize the flame, H₂ has a destabilizing effect which is the most dominant. A higher N₂ and CO₂ dilution fraction increased the range of equivalence ratios where unstable flames were obtained due to the increase in the thermal-diffusive instabilities.     

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.     

Laminar flame speed studies of lean premixed H2/CO/air flames

Laminar flame speeds of lean premixed H₂/CO/air mixtures were measured in the counterflow configuration over a wide range of H₂ content at lean conditions. The values were determined by extrapolating the referenced flame speed to zero stretch rate using the non-linear extrapolation method to reduce the systematic error. Detailed calculation of laminar flame speed was also conducted using PREMIX code coupled with three different kinetic models. In general, simulation results agreed well with the experimental data. Both the experimental and calculation results revealed that the laminar flame speeds of lean premixed H₂/CO/air mixtures increased with H₂ content significantly when H₂ content was small (?15%) and gradually when H₂ content was large (>15%).     

Explosion behavior of CH4/O2/N2/CO2 and H2/O2/N2/CO2 mixtures

In this work, the explosion behavior of stoichiometric CH₄/O₂/N₂/CO₂ and H₂/O₂/N₂/CO₂ mixtures has been studied both experimentally and theoretically at different CO₂ contents and oxygen air enrichment factors. Peak pressure, maximum rate of pressure rise and laminar burning velocity were measured from pressure time records of explosions occurring in a closed cylindrical vessel. The laminar burning velocity was also computed through CHEMKIN–PREMIX simulations.     

Role of CO2 in the CH4 oxidation and H2 formation during fuel-rich combustion in O2/CO2 environments

The effect of CO₂ reactivity on CH₄ oxidation and H₂ formation in fuel-rich O₂/CO₂ combustion where the concentrations of reactants were high was studied by a CH₄ flat flame experiment, detailed chemical analysis, and a pulverized coal combustion experiment. In the CH₄ flat flame experiment, the residual CH₄ and formed H₂ in fuel-rich O₂/CO₂ combustion were significantly lower than those formed in air combustion, whereas the amount of CO formed in fuel-rich O₂/CO₂ combustion was noticeably higher than that in air. In addition to this experiment, calculations were performed using CHEMKIN-PRO. They generally agreed with the experimental results and showed that CO₂ reactivity, mainly expressed by the reaction CO₂ + H → CO + OH (R1), caused the differences between air and O₂/CO₂ combustion under fuel-rich condition. R1 was able to advance without oxygen. And, OH radicals were more active than H radicals in the hydrocarbon oxidation in the specific temperature range. It was shown that the role of CO₂ was to advance CH₄ oxidation during fuel-rich O₂/CO₂ combustion. Under fuel-rich combustion, H₂ was mainly produced when the hydrocarbon reacted with H radicals. However, the hydrocarbon also reacted with the OH radicals, leading to H₂O production. In fact, these hydrocarbon reactions were competitive. With increasing H/OH ratio, H₂ formed more easily; however, CO₂ reactivity reduced the H/OH ratio by converting H to OH. Moreover, the OH radicals reacted with H₂, whereas the H radicals did not reduce H₂. It was shown that OH radicals formed by CO₂ reactivity were not suitable for H₂ formation. As for pulverized coal combustion, the tendencies of CH₄, CO, and H₂ formation in pulverized coal combustion were almost the same as those in the CH₄ flat flame.     

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.     

Chemical effects of added CO2 on the extinction characteristics of H2/CO/CO2 syngas diffusion flames

Chemical effects of added CO₂ on flame extinction characteristics are numerically studied in H₂/CO syngas diffusion flames diluted with CO₂. The two representative syngas flames of 80% H₂ + 20% CO and 20% H₂ + 80% CO are inspected according to the composition of fuel mixture diluted with CO₂ and global strain rate. Particular concerns are focused on impact of chemical effects of added CO₂ on flame extinction characteristics through the comparison of the flame characteristics between well-burning flames far from extinction limit and flames at extinction. It is seen that chemical effects of added CO₂ reduce critical CO₂ mole fraction at flame extinction and thus extinguish the flame at higher flame temperature irrespective of global strain rate. This is attributed by the suppression of the reaction rate of the principal chain branching reaction through the augmented consumption of H-atom from the reaction CO₂ + H→CO + OH. As a result the overall reaction rate decreases. These chemical effects of added CO₂ are similar in both well-burning flames far from extinction limit and flames at extinction. There is a mismatching in the behaviors between critical CO₂ mole fraction and maximum flame temperature at extinction. This anomalous phenomenon is also discussed in detail.     

HDMR correlations for the laminar burning velocity of premixed CH4/H2/O2/N2 mixtures

Correlations for the laminar burning velocity of premixed CH₄/H₂/O₂/N₂ mixtures were developed using the method of High Dimensional Model Representation (HDMR). Based on experiment data over a wide range of conditions reported in the literature, two types of HDMR correlation (i.e. global and piecewise HDMR correlations) were obtained. The performance of these correlations was assessed through comparison with experimental results and the correlation reported in the literature. The laminar burning velocity predicted by the piecewise HDMR correlations was shown to agree very well with those from experiments. Therefore, the piecewise HDMR correlations can be used as an effective replacement for the full chemical mechanism when the prediction of the laminar burning velocity is needed in certain combustion modeling.     

The synergistic effect of equivalence ratio and initial temperature on laminar flame speed of syngas

The laminar flame speed of syngas (CO:H₂ = 1:1)/air premixed gas in a wide equivalence ratio range (0.6–5) and initial temperature (298–423 K) was studied by Bunsen burner. The results show that the laminar flame speed first increases and then decreases as the equivalence ratio increasing, which is a maximum laminar flame speed at n = 2. The laminar flame speed increases exponentially with the increase of initial temperature. For different equivalent ratios, the initial temperature effects on the laminar flame speed is different. The initial temperature effects for n = 2 (the most violent point of the reaction) is lower than others. It is found that H, O and OH are affected more and more when the equivalence ratio increase. When the equivalence ratio is far from 2, the reaction path changes, and the influence of initial temperature on syngas combustion also changes. The laminar flame speed of syngas is more severely affected by H + O₂ = O + OH and CO + OH = CO₂ + H than others, which sensitivity coefficient is larger and change more greatly than others when the initial temperature and equivalence ratio change. Therefore, the laminar flame speed of syngas/air premixed gas is affected by the initial temperature and equivalence ratio. A new correlation is proposed to predict the laminar flame speed of syngas (CO:H₂ = 1:1)/air premixed gas under the synergistic effect of equivalence ratio and initial temperature (for equivalence ratios of 0.6–5, the initial temperature is 298–423 K).     

Catalytic conversion of CH4 and CO2 to synthesis gas on Ni/SiO2 catalysts containing Gd2O3 promoter

A series of Ni/SiO₂ catalysts containing different amounts of Gd₂O₃ promoter was prepared, characterized by H₂-adsorption and XRD, and used for carbon dioxide reforming of methane (CRM) and methane autothermal reforming with CO₂ + O₂ (MATR) in a fluidized-bed reactor. The results of pulse surface reactions showed that Ni/SiO₂ catalysts containing Gd₂O₃ promoter could increase the activity for CH₄ decomposition, and Raman analysis confirmed that reactive carbon species mainly formed on the Ni/SiO₂ catalysts containing Gd₂O₃ promoter. In this work, it was found that methane activation and reforming reactions proceeded according to different mechanisms after Gd₂O₃ addition due to the formation of carbonate species. In addition, Ni/SiO₂ catalysts containing Gd₂O₃ promoter demonstrated higher activity and stability in both CRM and MATR reactions in a fluidized bed reactor than Ni/SiO₂ catalysts without Gd₂O₃ even at a higher space velocity.     

The effects of composition on burning velocity and nitric oxide formation in laminar premixed flames of CH4 + H2 + O2 + N2

Experimental measurements of adiabatic burning velocity and NO formation in (CH₄ + H₂) + (O₂ + N₂) flames are presented. The hydrogen content in the fuel was varied from 0 to 35% and the oxygen content in the air from 20.9 to 16%. Nonstretched flames were stabilized on a perforated plate burner at 1 atm. The heat flux method was used to determine burning velocities under conditions when the net heat loss of the flame is zero. Adiabatic burning velocities of methane + hydrogen + nitrogen + oxygen mixtures were found in satisfactory agreement with the modeling. The NO concentrations in these flames were measured in the burnt gases at a fixed distance from the burner using probe sampling. In lean flames, enrichment by hydrogen has little effect on [NO], while in rich flames, the concentration of nitric oxide decreases significantly. Dilution by nitrogen decreases [NO] at any equivalence ratio. Numerical predictions and trends were found in good agreement with the experiments. Different responses of stretched and nonstretched flames to enrichment by hydrogen are demonstrated and discussed.     

Catalytic CO2 reforming of CH4 over Cr-promoted Ni/char for H2 production

The objective of the study is to investigate the catalytic performance of Cr-promoted Ni/char in CO₂ reforming of CH₄ at 850 °C. The char obtained from the pyrolysis of a long-flame coal at 1000 °C was used as the support. The catalysts were prepared by incipient wetness impregnation methods with different metal precursor doping sequence. The characterization of the composite catalysts was evaluated by XRD, XPS, SEM-EDS, TEM, H₂-TPR, CO₂-TPD, CH₄-TPSR, and CO₂-TPO. The results indicate that the catalyst prepared by co-impregnation of Ni and Cr possess higher activity than those by sequential impregnation. The optimal loading of Cr on 5 wt% Ni/char is 7.8 wt‰. Moreover, the molar feed ratio of CH₄/CO₂ has a considerable effect on both the stability and the activity of Cr–Ni/char. The main effect of Cr is the great enhance of the adsorption to CO₂. It is interesting that the conversions of CH₄ and CO₂ over Cr-promoted Ni/char and Ni/char decrease initially, following by a steady rise as the reaction proceeds with time-on-stream (TOS). In addition, cyclic tests were conducted and no distinct deterioration in the catalytic performance of the catalysts was observed. On the basis of the obtained results, nickel carbide was speculated to be the active species which was formed during the CO₂ reforming of CH₄ reaction.     

Flame characteristics in H2/CO synthetic gas diffusion flames diluted with CO2: Effects of radiative heat loss and mixture composition

Numerical study is conducted to understand the impact of fuel composition and flame radiation in flame structure and their oxidation process in H₂/CO synthetic gas diffusion flame with and without CO₂ dilution. The models of Sun et al. and David et al., which have been well known to be best-fitted for H₂/CO synthetic mixture flames, are evaluated for H₂/CO synthetic mixture flames diluted with CO₂. Effects of radiative heat loss to flame characteristics are also examined in terms of syngas mixture composition. Importantly contributing reaction steps to heat release rate are compared for the synthetic gas mixture flames of high contents of H₂ and CO, individually, with and without CO₂ dilution. The modification of the oxidation pathways is also addressed.     

Promotional effect of alkaline earth over Ni-La2O3 catalyst for CO2 reforming of CH4: Role of surface oxygen species on H2 production and carbon suppression

Alkaline earth elements (Mg, Ca and Sr) on Ni-La₂O₃ catalyst have been investigated as promoters for syngas production from dry CO₂ reforming of methane (DRM). The catalysis results of DRM performance at 600 °C show that the Sr-doped Ni-La₂O₃ catalyst not only yields the highest CH₄ and CO₂ conversions (∼78% and ∼60%) and highest H₂ production (∼42% by vol.) but also has the lowest carbon deposition over the catalyst surface. The XPS, O₂-TPD, H₂-TPR and FTIR results show that the excellent performance over the Sr-doped Ni-La₂O₃ catalyst is attributed to the presence of a high amount of lattice oxygen surface species which promotes C-H activation in DRM reaction, resulting in high H₂ production. Moreover, these surface oxygen species on the Ni-SDL catalyst can adsorb CO₂ molecules to form bidentate carbonate species, which can then react with the surface carbon species formed during DRM, resulting in higher CO₂ conversion and lower carbon formation.     

NOx emission characteristics of partially premixed laminar flames of H2/CO/CO2 mixtures

NO_x emission indices were experimentally measured for partially premixed laminar flames of five different H₂/CO/CO₂ fuels over a wide range of equivalence ratios. Through those fuels, the effects of H₂/CO ratio and CO₂ concentration on NO_x emissions, flame appearance, visible flame height and flame temperature are presented. EINO_x values increase when 1.0 ≤ Φ ≤ 1.6, then remain near the highest value, before decreasing slowly when 3.85 ≤ Φ ≤ ∞. The increase of the CO₂ concentration reduces the EINO_x for the whole range of equivalence ratios, while the increase in the H₂/CO ratio reduces the EINO_x when Φ ≤ 2.0 and is inconsequential for richer mixtures. The variation in flame temperatures approximates EINO_x trends. The variation of flame color from blue to orange when the H₂/CO ratio is increased might be explained by higher CO levels in by-product combustion.     

Effect of hydrogen on H2/CH4 flame structure of MILD combustion using the LES method

Large eddy simulation (LES) method is employed to investigate the effect of the hydrogen content of fuel on the H₂/CH₄ flame structure under the moderate or intense low-oxygen dilution (MILD) condition. The turbulence–chemistry interaction of the numerically unresolved scales is modelled using the PaSR method, where the full mechanism of GRI-2.11 represents the chemical reactions. The influence of hydrogen concentration on the flame structure is studied using the profiles of temperature, CH₂O and OH mass fractions and the diffusion profiles of un-burnt fuel through the flame front. Furthermore, more details are investigated by contours of OH, HCO and CH₂O radicals in an area near the nozzle exit zone. Results show that increasing the hydrogen content of fuel reinforces the MILD combustion zone and increases the peak value of the flame temperature and OH mass fraction. This increment also increases the flame thickness and reduces the OH oscillations and diffusion of the un-burnt fuel through the flame front.     

Experimental and numerical study on the effect of composition on laminar burning velocities of H2/CO/N2/CO2/air mixtures

Experimental and numerical study on laminar burning velocity of H₂/CO/N₂/CO₂/air mixtures was conducted by using a constant volume bomb and Chemkin package. Good agreement between experimental measurements and numerical calculations by using USCII Mech is achieved. Diffusional-thermal instability is enhanced but hydrodynamic instability is insensitive to the increase of hydrogen fraction in fuel mixtures. For mixtures with different hydrogen fractions, the adiabatic flame temperature is not the dominant influencing factor while high thermal diffusivity of hydrogen obviously enhances the laminar burning velocity. Laminar burning velocities increase with increasing hydrogen fraction and equivalence ratio (0.4–1.0). This is mainly due to the high reactivity of H₂ leading to high production rate of H and OH radicals. Reactions  and  play the dominant role in the production of H radical for mixtures with high hydrogen fraction, and reaction R31 plays the dominant role for mixtures with low hydrogen fraction.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

Effects of modifying Ni/Al2O3 catalyst with cobalt on the reforming of CH4 with CO2 and cracking of CH4 reactions

Alumina supported nickel (Ni/Al₂O₃), nickel–cobalt (Ni–Co/Al₂O₃) and cobalt (Co/Al₂O₃) catalysts containing 15% metal were synthesized, characterized and tested for the reforming of CH₄ with CO₂ and CH₄ cracking reactions. In the Ni–Co/Al₂O₃ catalysts Ni–Co alloys were detected and the surface metal sites decreased with decrease in Ni:Co ratio. Turnover frequencies of CH₄ were determined for both reactions. The initial turnover frequencies of reforming (TOF_DRM) for Ni–Co/Al₂O₃ were greater than that for Ni/Al₂O₃, which suggested a higher activity of alloy sites. The initial turnover frequencies for cracking (TOF_CRK) did not follow this trend. The highest average TOF_DRM, H₂:CO ratio and TOF_CRK were observed for a catalyst containing a Ni:Co ratio of 3:1. This catalyst also had the maximum carbon deposited during reforming and produced the maximum reactive carbon during cracking. It appeared that carbon was an intermediate product of reforming and the best catalyst was able to most effectively crack CH₄ and oxidize carbon to CO by CO₂.     

Preferential diffusion effects on flame characteristics in H2/CO syngas diffusion flames diluted with CO2

Numerical study is conducted to clarify preferential diffusion effects of H₂ and H on flame characteristics in synthetic diffusion flames of the compositions of 80% H₂/20% CO and 20% H₂/80% CO as representatively H₂-enriched and CO-enriched H₂/CO flames. Impacts of CO₂ addition to the flames are also examined through the variation of added CO₂ mole fraction from 0 to 0.5. A comparison was made by employing a mixture-averaged diffusivity and the suppression of the diffusivities of H and H₂. It is found that preferential diffusion effects on maximum flame temperature cannot be explained by the well-known behavior between maximum flame temperature and scalar dissipation rate but by chemical processes. The concrete evidence is also presented through the examination of the behavior of maximum H mole fraction and the behavior of importantly-contributing reaction steps to overall heat release rate.