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.     

The effects of hydrogen addition on Fenimore NO formation in low-pressure,fuel-rich-premixed,burner-stabilized CH4/O2/N2 flames

We investigate the effects of hydrogen addition on Fenimore NO formation in fuel-rich, low-pressure burner-stabilized CH₄/O₂/N₂ flames. Towards this end, axial profiles of temperature and mole fractions of CH and NO are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalent ratios of 1.3 and 1.5, using 0.25 mole fraction of hydrogen in the fuel, while varying the mass flux through the burner. The results are compared with those reported previously for burner-stabilized CH₄/O₂/N₂ flames. The increased burning velocity caused by hydrogen addition is seen to result in a lower flame temperature as compared to methane flame stabilized at the same mass flux. This increase in burner stabilization upon hydrogen addition results in significantly lower CH mole fractions at φ = 1.3, but appears to have little effect on the CH profile at φ = 1.5. In addition, the results show that not only the maximum flame temperature is reduced upon hydrogen addition, but the local gas temperature in the region of the CH profile is lowered as well. The measured NO mole fractions are seen to decrease substantially for both equivalence ratios. Analysis of the factors responsible for Fenimore NO formation shows the reduction in temperature in the flame front to be the major factor in the decrease in NO mole fraction, with a significant contribution from the decrease in CH mole fraction at φ = 1.3. At φ = 1.5, the results suggest that the lower flame temperature upon hydrogen addition further retards the conversion of residual fixed-nitrogen species to NO under these rich conditions as compared to the equivalent methane flames.     

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.     

Numerical and experimental analysis of NO emissions from a lab-scale burner fed with hydrogen-enriched fuels and operating in MILD combustion

An experimental and computational investigation of a lab-scale burner, which can operate in both flame and MILD combustion conditions and is fed with methane and a methane/hydrogen mixture (hydrogen content of 60% by vol.), is carried out. The modelling results indicate the need of a proper turbulence/chemistry interaction treatment and rather detailed kinetic mechanisms to capture MILD combustion features, especially in presence of hydrogen. Despite these difficulties, Computational Fluid Dynamics results to be very useful, as for instance it allows evaluating the internal recirculation degree in the burner, a parameter which is otherwise difficult to be determined. Moreover the model helps interpreting experimental evidences: for instance the modelling results indicate that in presence of hydrogen the NNH and N₂O intermediate routes are the dominant formation pathways for the MILD combustion conditions investigated.     

A numerical study on NOx formation in laminar counterflow CH4/air triple flames

Formation of NO_x in counterflow methane/air triple flames at atmospheric pressure was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. Results indicate that in a triple flame, the appearance of the diffusion flame branch and the interaction between the diffusion flame branch and the premixed flame branches can significantly affect the formation of NO_x, compared to the corresponding premixed flames. A triple flame produces more NO and NO₂ than the corresponding premixed flames due to the appearance of the diffusion flame branch where NO is mainly produced by the thermal mechanism. The contribution of the N₂O intermediate route to the total NO production in a triple flame is much smaller than those of the thermal and prompt routes. The variation in the equivalence ratio of the lean or rich premixed mixture affects the amount of NO formation in a triple flame. The interaction between the diffusion and the premixed flame branches causes the NO and NO₂ formation in a triple flame to be higher than in the corresponding premixed flames, not only in the diffusion flame branch region but also in the premixed flame branch regions. However, this interaction reduces the N₂O formation in a triple flame to a certain extent. The interaction is caused by the heat transfer and the radical diffusion from the diffusion flame branch to the premixed flame branches. With the decrease in the distance between the diffusion flame branch and the premixed flame branches, the interaction is intensified.     

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.     

H2 effects on diesel combustion and emissions with an LPL-EGR system

In this study, we examined H₂ effects on the combustion and emissions of a diesel engine with low-pressure loop (LPL) exhaust gas recirculation (EGR). We converted a 2.2-L four-cylinder direct-injection diesel engine satisfying Euro5 for H₂ supply. An LPL-EGR system replaced the high-pressure loop (HPL) EGR system. For all tests, the brake mean effective pressure (BMEP) was kept at 4 bar and the EGR ratio was varied from 9 to 42%. The H₂ energy percentage was varied from 0 to 7.4% independently to evaluate the H₂ effects and EGR effects separately. The heat release rate was calculated from the measured cylinder pressure. We found that substitution of H₂ for diesel fuel made the premixed burn fraction larger, and reduced the nitrous oxide (NOx) and particulate matter (PM) emissions simultaneously. For example, the NOx emissions were reduced by 36% for an EGR of 42% and an H₂ percentage of 7.4%. PM emissions were reduced by 18% for an EGR of 35% and an H₂ percentage of 7.4% compared with diesel fuel only cases.     

NOx formation and reduction mechanisms in staged O2/CO2 combustion

The purpose of this study was to investigate the NO_x formation and reduction mechanisms in staged O₂/CO₂ combustion and in air combustion. A flat CH₄ flame doped with NH₃ for fuel-N was formed over the honeycomb, and NO_x formation characteristics were investigated. In addition, chemiluminescence of OH^* distribution was measured, and CHEMKIN-PRO was used to investigate the detailed NO_x reduction mechanism. In general, the NO_x conversion ratio decreases with decreasing primary O₂/CH₄ ratio, whereas NH₃ and HCN, which are easily converted to NO_x in the presence of O₂, increases rapidly. Therefore, a suitable primary O₂/CH₄ ratio exists in the staged combustion. Our experiments showed the primary O₂/CH₄ ratio, which gave the minimum fixed nitrogen compounds in O₂/CO₂ combustion, was lower than in air combustion. The NO_x conversion ratio in O₂/CO₂ combustion was lower than in air combustion by 40% in suitable staged combustion. This could be explained by high CO₂ concentrations in the O₂/CO₂ combustion. It was shown that abundant OH radicals were formed in O₂/CO₂ combustion through the CO₂ + H → CO + OH, experimentally and numerically. OH radicals produced H and O radicals through H₂ + OH → H + H₂O and O₂ + H → OH + O, because a mass of hydrogen source exists in the CH₄ flame. O and OH radicals formed in the fuel-rich region enhanced the oxidation of NH₃ and HCN. NO_x formed by the oxidation of NH₃ and HCN was converted to N₂ because the oxidation occurred in the fuel-rich region where the NO_x reduction effect was high. In fact, the oxidation of NH₃ and HCN in the fuel-rich region was preferable to remaining NH₃ and HCN before secondary O₂ injection in the staged combustion. A significant reduction in NO_x emission could be achieved by staged combustion in O₂/CO₂ combustion.     

Sensitizing effects of NOx on CH4 oxidation at high pressure

The CH₄/O₂/NO_x system is investigated in a laboratory-scale high pressure laminar flow reactor with the purpose of elucidating the sensitizing effects of NO_x on CH₄ oxidation at high pressures and medium temperatures. Experiments are conducted at 100, 50, and 20 bar, 600-900 K, and stoichiometric ratios ranging from highly reducing to oxidizing conditions. The experimental results are interpreted in terms of a detailed kinetic model drawn from previous work of the authors, including an updated reaction subset for the direct interactions of NO_x and C_1-2 hydrocarbon species relevant to the investigated conditions. The results reveal a significant decrease in the initiation temperature upon addition of NO_x. A similar effect is observed with increasing pressure. The sensitizing effect of NO_x is related to the hydrocarbon chain-propagating NO/NO₂ cycle operated by NO₂+CH₃?NO+CH₃O and NO+CH₃OO?NO₂+CH₃O as well as the formation of chain-initiating OH radicals from interactions between NO/NO₂ and the H/O radical pool. At low temperatures, reactions between NO/NO₂ and CH₃O/CH₂O also gain importance. The results indicate a considerable intermediate formation of nitromethane (CH₃NO₂) as a characteristic high-pressure phenomenon. The formation of CH₃NO₂ represents an inactivation of NO_x, which may result in a temporary reduction of the overall hydrocarbon conversion rate.     

Flameless combustion for hydrogen containing fuels

In this paper, flameless combustion was promoted to suppress thermal-NO_x formation in the hydrogen-high-containing fuel combustion. The PSRN model was used to model the flameless combustion in the air for four fuels: H₂/CH₄ 60/40% (by volume), H₂/CH₄ 40/60%, H₂/CH₄ 20/80% and pure hydrogen. The results show that the NO_x emissions below 30 ppmv while CO emissions are under 50 ppmv, which are coincident with the experimental data in the “clean flameless combustion” regime for all the four fuels. The simulation also reveals that CO decreases from 48 ppmv to nearly zero when the hydrogen composition varies from 40% to 100%, but the NO_x emission is not sensitive to the hydrogen composition. In the highly diluted case, the NO_x and CO emissions do not depend on the entrainment ratio.     

An experimental investigation of NO2 emission characteristics of a heavy-duty H2-diesel dual fuel engine

This paper investigated the nitrogen dioxide (NO₂) emissions of a heavy-duty diesel engine operated in hydrogen (H₂)-diesel dual fuel combustion mode with H₂ supplemented into the intake air. Preliminary measurements using the 13-mode European Stationary Cycle (ESC) demonstrated the significant effect of H₂ addition on the emissions of NO₂. The detailed effects of H₂ addition and engine load on NO₂ emissions were examined at 1200 RPM. The addition of a small amount of H₂ increased substantially the emissions of NO₂ and the NO₂/NO_x ratio, especially at low load. Increasing the engine load was found to inhibit the enhancing effect of H₂ on the conversion of NO to NO₂ with the maximum NO₂/NO_x ratio observed at lower H₂ concentration. The maximum NO₂ emissions of the H₂-diesel dual fuel operation were three (at 70% load) to five (at 10% load) times that of diesel operation. Further increasing the addition of H₂ beyond the point with maximum NO₂ emissions still produced more NO₂ than for diesel-only operation. Based on the experimental data obtained, the engine load and maximum averaged bulk mixture temperature were not the main factors dominating the formation of NO₂ in the H₂-diesel dual fuel engine. A preliminary analysis demonstrated the significant effect of the unburned H₂ on NO₂ emissions. When mixed with the hot combustion product, the unburned H₂ that survived the main combustion process might further oxidize to raise the HO₂ levels and enhance the conversion of NO to NO₂. In comparison, the changes in the combustion process including the start of combustion, combustion duration and maximum heat release rate may not contribute substantially to the increased NO₂ emissions observed.     

Modeling fuel NOx formation from combustion of biomass-derived producer gas in a large-scale burner

This study investigates the characteristics of fuel NO_x formation resulting from the combustion of producer gas derived from biomass gasification using different feedstocks. Common industrial burners are optimized for using natural gas or coal-derived syngas. With the increasing demand in using biomass for power generation, it is important to develop burners that can mitigate fuel NO_x emissions due to the combustion of ammonia, which is the major nitrogen-containing species in biomass-derived gas. In this study, the combustion process inside the burner is modeled using computational fluid dynamics (CFD) with detailed chemistry. A reduced mechanism (36 species and 198 reactions) is developed from GRI 3.0 in order to reduce the computation time. Combustion simulations are performed for producer gas arising from different feedstocks such as wood gas, wood + 13% DDGS (dried distiller grain soluble) gas and wood + 40% DDGS gas and also at different air equivalence ratios ranging from 1.2 to 2.5. The predicted NO_x emissions are compared with the experimental data and good levels of agreement are obtained. It is found out that NO_x is very sensitive to the ammonia content in the producer gas. Results show that although NO–NO₂ interchanges are the most prominent reactions involving NO, the major NO producing reactions are the oxidation of NH and N at slightly fuel rich conditions and high temperature. Further analysis of results is conducted to determine the conditions favorable for NO_x reduction. The results indicate that NO_x can be reduced by designing combustion conditions which have fuel rich zones in most of the regions. The results of this study can be used to design low NO_x burners for combustion of gas mixtures derived from gasification of biomass. One suggestion to reduce NO_x is to produce a diverging flame using a bluff body in the flame region such that NO generated upstream will pass through the fuel rich flame and be reduced.     

Mesoporous CexMn1−xO2 composites as novel alternative carriers of supported Co3O4 catalysts for CO preferential oxidation in H2 stream

The mesoporous Co₃O₄ supported catalysts on Ce–M–O (M = Mn, Zr, Sn, Fe and Ti) composites were prepared by surfactant-assisted co-precipitation with subsequent incipient wetness impregnation (SACP–IWI) method. The catalysts were employed to eliminate trace CO from H₂-rich gases through CO preferential oxidation (CO PROX) reaction. Effects of M type in Ce–M–O support, atomic ratio of Ce/(Ce + Mn), Co₃O₄ loading and the presence of H₂O and CO₂ in feed were investigated. Among the studied Ce–M–O composites, the Ce–Mn–O is a superior carrier to the others for supported Co₃O₄ catalysts in CO PROX reaction. Co₃O₄/Ce_0.9Mn_0.1O₂ with 25 wt.% loading exhibits excellent catalytic properties and the 100% CO conversion can be achieved at 125–200 °C. Even with 10 vol.% H₂O and 10 vol.% CO₂ in feed, the complete CO transformation can still be maintained at a wide temperature range of 190–225 °C. Characterization techniques containing N₂ adsorption/desorption, X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR) and scanning electron microscopy (SEM) were employed to reveal the relationship between the nature and catalytic performance of the developed catalysts. Results show that the specific surface area doesn’t obviously affect the catalytic performance of the supported cobalt catalysts, but the right M type in carrier with appropriate amount effectively improves the Co₃O₄ dispersibility and the redox behavior of the catalysts. The large reducible Co³⁺ amount and the high tolerance to reduction atmosphere resulted from the interfacial interaction between Co₃O₄ and Ce–Mn support may significantly contribute to the high catalytic performance for CO PROX reaction, even in the simulated syngas.     

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.     

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.     

Studies on B sites in Fe-doped LaNiO3 perovskite for SCR of NOx with H2

A series of LaNi_1−xFe_xO₃ (x = 0.0, 0.2, 0.4, 0.7, and 1.0) perovskites were synthesized and characterized by X-ray diffraction (XRD), N₂ physisorption, scanning electron microscopy (SEM), H₂-temperature-programmed reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS). The perovskites were investigated for selective catalytic reduction of NO_x by hydrogen (H₂-SCR). It is shown that Fe addition into LaNiO₃ leads to a promoted efficiency of NO_x removal, as well as a high stability of perovskite structure. Moreover, easy reduction of Ni³⁺ to Ni²⁺ with the aid of appropriate Fe component mainly accounts for the enhanced activity. Meanwhile, deactivation of the sulfated catalysts is due to that sulfates mainly deposit on active Ni component while doping of Fe can protect Ni to some extent at the expense of partial sulfation.     

CNT/PDMS composite membranes for H2 and CH4 gas separation

Polydimethylsiloxane (PDMS) composites with different weight amounts of multi-walled carbon nanotubes (MWCNT) were synthesised as membranes to evaluate their gas separation properties. The selectivity of the membranes was investigated for the separation of H₂ from CH₄ gas species. Membranes with MWCNT concentrations of 1% increased the selectivity to H₂ gas by 94.8%. Furthermore, CH₄ permeation was almost totally blocked through membranes with MWCNT concentrations greater than 5%. Vibrational spectroscopy and X-ray photoelectron spectroscopy techniques revealed that upon the incorporation of MWCNT a decrease in the number of available Si–CH₃ and Si–O bonds as well as an increase in the formation of Si–C bonds occurred that initiated the reduction in CH₄ permeation. As a result, the developed membranes can be an efficient and low cost solution for separating H₂ from larger gas molecules such as CH₄.     

Enhancement of the H2 desorption properties of LiAlH4 doping with NiCo2O4 nanorods

Lithium aluminum hydride (LiAlH₄) is considered as an attractive candidate for hydrogen storage owing to its favorable thermodynamics and high hydrogen storage capacity. However, its reaction kinetics and thermodynamics have to be improved for the practical application. In our present work, we have systematically investigated the effect of NiCo₂O₄ (NCO) additive on the dehydrogenation properties and microstructure refinement in LiAlH₄. The dehydrogenation kinetics of LiAlH₄ can be significantly increased with the increase of NiCo₂O₄ content and dehydrogenation temperature. The 2 mol% NiCo₂O₄-doped LiAlH₄ (2% NCO–LiAlH₄) exhibits the superior dehydrogenation performances, which releases 4.95 wt% H₂ at 130 °C and 6.47 wt% H₂ at 150 °C within 150 min. In contrast, the undoped LiAlH₄ sample just releases <1 wt% H₂ after 150 min. About 3.7 wt.% of hydrogen can be released from 2% NCO–LiAlH₄ at 90 °C, where total 7.10 wt% of hydrogen is released at 150 °C. Moreover, 2% NCO–LiAlH₄ displayed remarkably reduced activation energy for the dehydrogenation of LiAlH₄.     

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.