Lean Methane Research Articles

Scaling transition of turbulent flame speed for thermodiffusively unstable flames

This work presents an experimental set of Bunsen flames characterized by a moderate Reynolds number and a variable turbulence intensity. Ten lean hydrogen-enriched methane–air mixtures at three turbulence levels are investigated, ranging from methane–air to hydrogen–air mixtures. Such mixtures are selected to have an almost constant laminar flame speed while inducing the onset of thermal-diffusive (TD) instability by gradually increasing the hydrogen content of the blend. The flames' global consumption speed, stretch factor, and flame surface area are investigated and discussed as functions of the effective Lewis number of the mixture. As the interplay between TD instability and turbulence enhances the overall flame propagation, below a transitional Lewis number, flames are observed to be particularly sensitive to external turbulent forcing. This synergistic interaction is discussed in terms of Karlovitz and Lewis numbers. A parameterization of the turbulent flame speed is thus proposed, based on a functional form depending, concurrently, on both Karlovitz and Lewis numbers. The proposed form is shown to fit the experimental results at different turbulence levels and to capture the flame speed enhancement across the transitional Lewis number.

Incorporating Si into NiO support to facilitate oxygen activation for CH4 combustion

In this study, high-performance Pd/NiO-Si catalysts for lean methane oxidation were synthesized using the solution combustion and impregnation method. The incorporation of silicon in NiO promoted the generation of Ni2+ and strengthened the metal-support interaction. This enhanced interaction promoted the generation and movement of active oxygen species on surface, which are essential for maintaining Pd species in an active oxidized state, thereby ensuring the effective activation of CH4. The Pd/NiO-Si catalyst with an optimal amount of Si exhibited an excellent catalytic performance, achieving a T90 of 440 °C for methane oxidation under wet conditions. The elemental doping strategy in this study, which significantly enhances the production of highly active oxygen species with strong mobility, plays a crucial role in the effective utilization of precious metals such as Pd.

Numerical investigation of lean methane flame response to NRP discharges actuation

This study investigates the response of a laminar methane-air flame to Nanosecond Repetitively Pulsed (NRP) discharges in a canonical wall-stabilized burner using a combined experimental and numerical approach. The flow and flame behaviors were modeled using Direct Numerical Simulation (DNS) with an Analytically Reduced Chemistry for a precise chemical description. A phenomenological model incorporating detailed plasma kinetics and experimental observations was developed to simulate plasma effects. Zero-dimensional plasma reactor simulations were used to build up a reduced-order model describing discharge energy distribution in the specific conditions studied. Experimental measurements of electrical profiles identified two discharge regimes: a low-energy Corona discharge and a higher-energy Glow discharge, characterized by distinct spatial energy distributions. Experimental flame response analysis revealed three major phases: marginal response up to 100 pulses, a downstream shift of the flame tip, and stabilization after 400 pulses. Numerical simulations indicated that the Corona regime is crucial for explaining initial flame responses, while the Glow regime influences later stages. Adjustments in the Vibrational-Translational (VT) energy relaxation time and energy deposition ratios between fresh and burnt gases were necessary to match experimental observations. Additionally, an accurate modeling of the transient and steady-state flame responses requires integrating both the specificity of the Corona and the Glow discharge regimes. Future work should focus on measuring or theoretically calculating N2(v) relaxation times in CH4-H2O-CO2 mixtures and analyzing the spatial energy distribution of discharges interacting with flames to enhance plasma-combustion coupled models.Novelty and significanceIn this work, a phenomenological plasma-assisted combustion model has been developed, to investigate a laminar premixed stagnation plate burner, focusing on VT energy relaxation time and spatio-temporal energy distribution modeling. For the first time, not only O2, N2 and O but also the fuel and combustion intermediates and products have been considered in the VT relaxation model. It revealed their strong influence on the overall flame response in a case where the discharge crosses a flame front, highlighting the strong beneficial effect of energy deposited in vibrational form. The study questions and investigates the energy distribution from fresh to burnt gases, challenging the conventional uniform energy distribution assumption. The experimental identification of two specific plasma regimes was necessary to predict the transient flame response. Additionally, energy deposited downstream of the flame, in fresh gases, was found to more efficient than in hot gases to enhance combustion.

Innovative Fixed-Bed Reactor Integrated with Heat Transfer System for Lean Methane Mixture Removal

A new type of compact, portable fixed-bed reactor integrated with a heat transfer system was developed for the removal of volatile and flammable air pollutants such as lean methane and volatile organic compounds (VOCs). The reactor may operate in catalytic or thermal combustion conditions with the purpose of achieving autothermal processes with the possibility of energy recovery. An excess heat recovery point was designed behind the reactor bed at the place where the gas temperature is the highest to enable its usage. The mathematical model is presented together with a number of simulation calculations performed for the assessment of the developed reactor. The case study in this paper was for catalytic methane oxidation at a temperature of 400 °C, a methane concentration between 0.1% and 2% by weight, a gas flow rate of 1 m3/s STP, and a heat exchange surface for the assumed plate exchanger from 10 to 200 m2. The calculations show that the thickness of the insulation is of little importance for the operation of the equipment, and a sufficient thickness was about 20–50 mm. The optimal area for the considered case is 80–100 m2. It was found that recovery of thermal energy is possible only for higher methane concentrations, above 0.3% by weight. Using an appropriate surface for the exchanger, it is possible to recover even 50% of the combustion enthalpy at a methane concentration of 0.45% by weight. For an exchanger area below 50 m2, the recoverable energy drops rapidly. It was found that the exchanger area is the most important equipment parameter under consideration.

Advancing catalytic oxidation of lean methane over cobalt-manganese oxide via a phase-engineered amorphous/crystalline interface.

CoMnOx catalysts were prepared using a microwave (MW)/ultrasonic (US)-assisted method. Amorphous/crystalline regions in CoMnOx (MW = 250 W US = 300 W) increased the oxygen vacancy content and CoMnOx exhibited excellent activity for methane oxidation (T90 = 330 °C). A new approach is provided here to improve the activity of transition metal catalysts.

Oxidation of lean methane by dielectric barrier discharge plasma and Mn–Ce catalyst

The synergistic dielectric barrier discharge plasma and Mn-Ce catalysts are employed to facilitate the low temperature and highly efficient oxidation of lean methane. The effect of the catalyst alone, plasma alone, and their synergistic effect on CH4 conversion are experimentally analyzed. It shows that the CH4 conversion rate under plasma catalysis is more than three times that of catalyst alone and plasma alone, with a maximum of 66.7% at 375 °C and 21 W, revealing a significant synergistic effect of plasma catalysis. The influence of Mn/Ce mass ratios (11Mn/Ce and 45Mn/Ce) and operational conditions (CH4/O2 molar ratio, preheating temperature, and discharge power) on CH4 conversion by plasma catalysis are also investigated. The CH4 conversion rate increases with the decrease of the CH4/O2 molar ratio and the increase in preheating temperature and discharge power. Meanwhile, the Mn/Ce mass ratio affects the CH4 oxidation and the synergistic effect of plasma catalysis. The oxidation activity of the 11Mn/Ce catalyst is mostly affected by the power at the preheating temperature below 325 °C. However, the 45Mn/Ce catalyst is affected by both preheating temperature and power. In addition, as the discharge power increases, the CH4 conversion rate exhibits a linear increase for 11Mn/Ce but exponential for 45Mn/Ce.

Transition to oscillatory instability of lean methane–air flames in microchannels

Micro-flow reactors and porous media burners are prone to instability in the form of flame with repetitive extinction and ignition (FREI) near the region of a temperature gradient. Although significant progress has been made in this field, there is still a lack of understanding regarding the nature of such stable-to-unstable transition. Some studies reported a smooth and continuous instability transition in microchannels, interpreting this phenomenon as a supercritical bifurcation. Meanwhile, others have observed that the transition is subcritical, with rapid, stepwise evolution of the stable flame to FREI. This study aims to rigorously determine the transition character theoretically and numerically using a two-dimensional model with a precise resolution of the bifurcation parameter (flow velocity) near the critical point and gradual wall temperature ramp. The results indicate that the transition is a subcritical bifurcation with strong hysteresis. However, the amplitude of the limit cycle born in the bifurcation point could be small compared to FREI-like oscillations. Moreover, further development of the instability depends significantly on the channel width. In relatively wide channels, the stable regime transforms immediately into the extinction/ignition one with rapid growth in amplitude. In moderate channels, complex transitional dynamics were observed with an evident pulsating regime, which evolved into FREI through mixed-mode oscillations. In narrow channels, the amplitude of transitional pulsating flame becomes comparable to the fully-developed extinction/ignition cycles, and the bifurcation diagram has a continuous character with no significant jumps or discontinuities. Such qualitative variation of transition character provides a possible explanation for contradictory interpretations presented in the literature.Novelty and Significance StatementCurrently, there is no consensus about the character of transition between the stable and extinction/ignition regimes in microchannels. Some studies have reported a continuous instability transition with an evident pulsating regime, interpreting it as a supercritical bifurcation, while others have observed subcritical bifurcation with a rapid transition. The novelty of this research lies in the rigorous determination of the bifurcation type and further instability development in microchannels of different widths based on an accurate simulation of flame dynamics near the critical point with very small steps of the flow velocity variation, along with the bifurcation theory. The study contributes to understanding the instability transition nature and may explain the different interpretations of the transitional phenomenon found in the literature. The results offer valuable insights for designing micro-scale and porous media combustion devices.

Electron transferring with oxygen defects on Ni-promoted Pd/Al2O3 catalysts for low-temperature lean methane combustion

Methane (CH4) is the second most consequential greenhouse gas after CO2, with a substantial global warming potential. The CH4 catalytic combustion offers an efficient method for the elimination of CH4. However, improving the catalytic performance of Pd-based materials for low-temperature CH4 combustion remains a big challenge. In this study, we synthesized an enhanced Pd/5NiAlOx catalyst that demonstrated superior catalytic activity and improved water resistance compared to the Pd/Al2O3 catalyst. Specifically, the T90 was decreased by over 100 °C under both dry and wet conditions. Introducing Ni resulted in an enormously enhanced number of oxygen defects on the obtained 5NiAlOx support. This defect-rich support facilitates the anchoring of PdO through increased electron transfer, thereby inhibiting the production of high-valence Pd(2+δ)+ and stimulating the generation of unsaturated Pd sites. Pd0 can effectively activate surface oxygen and PdO plays a significant role in activating CH4, resulting in high activity for Pd/5NiAlOx. On the other hand, the increased water resistance of Pd/5NiAlOx was mainly due to the generation of *OOH species and the lower accumulation of surface -OH species during the reaction process.

Evaluation of hydrogen/ammonia substitute fuel mixtures for methane: Effect of differential diffusion

One strategy for utilizing ammonia as an energy vector is to replace conventional hydrocarbons with hydrogen-enriched ammonia in existing or retrofitted combustors. However, the strong differential diffusion effect of hydrogen can significantly alter the combustion properties and cause challenges in combustor operability. Therefore, this numerical study performs a systematic investigation on the effect of differential diffusion on fundamental combustion properties of ammonia/hydrogen fuel blends. The investigated combustion properties span from the initiation of combustion, i.e., ignition, to stretched flame propagation and ultimately to flame stabilization mechanisms. The objective is to evaluate the feasibility of hydrogen/ammonia/air mixtures as substitutes for methane/air particularly considering the implications of differential diffusion effects. To this end, four fuel blends with similar unstretched burning properties are selected: fuel lean ammonia/hydrogen (AH-L), fuel rich ammonia/hydrogen (AH-R), fuel lean methane (M-L) and fuel lean methane/hydrogen (MH-L). First, the forced ignition and stretched flame propagation are evaluated. It is found that the AH-L (AH-R) mixture has a large negative (positive) Markstein length, and thereby among the selected fuel blends, AH-L (AH-R) has the lowest (highest) minimum ignition energy. Then flame stabilization mechanisms are investigated. For a stable flame, AH-L (AH-R) has an intensified (weakened) flame base and a weak (strong) flame tip, which shows a higher flashback (blow-off) propensity. Based on the critical gradient theory, a novel stability regime diagram is proposed. With the regime diagram, the flame stabilization limits (central flashback, boundary layer flashback, stable, and blow-off) and flow conditions can be determined for burners of different sizes.

Methane Combustion Kinetics over Palladium-Based Catalysts: Review and Modelling Guidelines

Fugitive methane emissions account for a significant proportion of greenhouse gas emissions, and their elimination by catalytic combustion is a relatively easy way to reduce global warming. New and novel reactor designs are being considered for this purpose, but their correct and efficient design requires kinetic rate expressions. This paper provides a comprehensive review of the current state of the art regarding kinetic models for precious metal catalysts used for the catalytic combustion of lean methane mixtures. The primary emphasis is on relatively low-temperature operation at atmospheric pressure, conditions that are prevalent in the catalytic destruction of low concentrations of methane in emission streams. In addition to a comprehensive literature search, we illustrate a detailed example of the methodology required to determine an appropriate kinetic model and the constants therein. From the wide body of literature, it is seen that the development of a kinetic model is not necessarily a trivial matter, and it is difficult to generalize. The model, especially the dependence on the water concentration, is a function of not only the active ingredients but also the nature of the support. Kinetic modelling is performed for six catalysts, one commercial and five that were manufactured in our laboratory, for illustration purposes.

Deep understanding the formation of MnCoOx in-situ grown on foam nickel towards efficient lean methane catalytic oxidation

Methane is the second largest greenhouse gas in the world, with a stronger greenhouse effect than carbon dioxide. The efficient elimination of methane in the atmosphere has important engineering significance in slowing down global temperature rise, energy resource utilization, collaborative control of pollutants, and promoting technological innovation. In this work, a general hydrothermal synthesis method was introduced to in-situ construct four different morphologies of MnCoOx (including rod-, spherical-, filamentous- and bulk-shape) on foam nickel (NF). The synthesis of MnCoOx/NF with different morphologies was due to changes in NF pretreatment conditions and precipitants, which affected the nucleation and growth rates of MnCoOx, ultimately resulting in different morphologies. When the four different morphologies of MnCoOx/NF were used as catalysts for lean methane catalytic oxidation, MnCoOx/NF-r exhibited the best excellent catalytic activity, and the T90 occurred at 428 °C in space velocity of 48,000 mL g−1 h−1. Such an outstanding performance was attributed to the unique properties of the MnCoOx/NF-r including the larger surface area and more oxygen vacancies for providing more active sites and a higher oxygen migration rate, which was very beneficial for improving the catalytic oxidation performance of methane.

Morphology engineering of Co3O4 spinel for efficient oxidation of lean methane at low temperature

Nowadays, the development of high-performance non-noble metal catalysts is an important research direction for controlling methane emissions from liquefied natural gas (LNG)-powered vehicles and vessels, and Co3O4 spinel has attracted great attention. In this work, Co3O4 catalysts with different morphologies (flower, sheet, particle, and cube) were synthesized by hydrothermal method and their catalytic performance was evaluated. The results showed that the flower-like Co3O4 (Co3O4-F) catalyst exhibited the highest activity in the lean methane oxidation with the T90 (temperature at the methane conversion of 90%) of 365 °C. Compared to other catalysts, Co3O4-F contained an amount of Co3+ sites and the weakest Co3+-O bond, which facilitated the extraction of active lattice oxygen and the initial oxidation of methane to intermediate products (formate and -COO-) on the catalyst surface. Meanwhile, the abundant oxygen vacancies on the surface of the Co3O4 catalyst could efficient activate O2 to form active oxygen species, which promoted the oxidation of intermediate products to CO2 and H2O. The methane oxidation over the Co3O4-F was confirmed to conform with Mars-van Krevelen mechanism. This work provides a facile way to enhance the methane oxidation activity of Co3O4 catalysts by modulating the morphology.

Dynamic behaviors and heat recovery with hot gas withdrawal of flow reversal reactor for thermal oxidation of lean methane

Dynamic behaviors and heat recovery with hot gas withdrawal of flow reversal reactor for thermal oxidation of lean methane

Thermally stable Pd/CeO2@SiO2 with a core-shell structure for catalytic lean methane combustion.

Noble metal catalysts exhibit high catalytic activity in lean CH4 combustion at low temperatures. However, the high surface energy of noble metal nanoparticles makes them susceptible to deactivation due to migratory-aggregation during the catalytic process. Herein, a core-shell structure with a Pd/CeO2 core and a SiO2 shell (denoted as Pd/CeO2@SiO2) was designed and prepared to enhance the thermal stability for catalytic lean CH4 combustion. A series of characterization methods demonstrated the successful encapsulation of SiO2 and the modified thermal stability. The results of activity tests indicated that Pd/CeO2@SiO2 exhibited the optimal catalytic performance. After seven runs, Pd/CeO2@SiO2 achieved 90% conversion of CH4 at 385 °C compared to Pd/CeO2 at 440 °C. The remarkable catalytic performance was attributed to the synergistic effect of strengthened metal-support interactions and the core-shell structure. On the one hand, the migration and aggregation of Pd nanoparticles were limited due to the protection of the SiO2 shell layer. On the other hand, the SiO2 shell layer further enhanced the interactions between the Pd nanoparticles and CeO2, thus promoting the formation of PdxCe1-xO2-δ solid solutions and active oxygen species, which were beneficial for the improvement of the stability and redox capacity of the catalyst.

Study in mitigation of lean methane and stable heat recovery via embedded heat exchanger tubes in the regenerative monolith bed

Study in mitigation of lean methane and stable heat recovery via embedded heat exchanger tubes in the regenerative monolith bed

Construction of Co/Mn-based nanowires with adjustable surface state for boosting lean methane catalytic oxidation

In this paper, CoMn based nanowires were in-situ grown on foam nickel by hydrothermal method combined with calcination treatment, and a monolithic methane oxidation catalyst was obtained. The effects of hydrothermal temperature and calcination temperature on the crystal structure, micro morphology and catalytic performance of the catalysts were systematically studied. The results indicated that when the hydrothermal temperature was 160 °C and the calcination temperature was 350 °C, Mn doped Co3O4 nanowires with uniform morphology can be obtained, accompanied by the appearance of CoMn2O4. The introduction of Mn ions caused lattice distortion of Co3O4, achieving the regulation of adsorbed oxygen and lattice oxygen. The monolithic MnCoO/NF–H-160 °C catalyst showed the best catalytic activity (T90 = 414 °C) for lean methane catalytic oxidation, which even surpassed the noble metal based catalyst. Its excellent catalytic activity was due to the fact that the catalyst can expose more active sites, rich active oxygen and good mass transfer characteristics. This study provides a new approach for designing efficient monolithic catalysts and has significant potential for application and development in the field of organic waste gas treatment.

Catalytic combustion of lean methane over different Co3O4 nanoparticle catalysts

Three types of Co3O4 catalyst, namely Co3O4 nanoparticles (denoted as Co3O4-NPs, ∼12 nm in diameter), Co3O4 nanoparticles encapsulated in mesoporou s SiO2 (denoted as Co3O4@SiO2), and Co3O4 nanoparticles inside microporous SiO2 hollow sub-microspheres (denoted as Co3O4-in-SiO2), were explored to catalyze the combustion of lean methane. It was found that the methane conversion over the three catalysts has the order of Co3O4-NPs ≈ Co3O4@SiO2 > Co3O4-in-SiO2 due to the different catalyst structure. The comparison experiments at high temperatures indicate the Co3O4@SiO2 has a significantly improved anti-sintering performance. Combined with the TEM and BET measurements, the results prove that the presence of the mesoporous SiO2 layer can maintain the catalytical activity and significantly improve the anti-sintering performance of Co3O4@SiO2. In contrast, the microporous SiO2 layer reduces the catalytical activity of Co3O4-in-SiO2 possibly due to its less effective diffusion path of combustion product. Thus, the paper demonstrates the pore size of SiO2 layer and catalyst structure are both crucial for the catalytical activity and stability.

Facet-dependently interfacial hybridization stabilized trivalent cerium species and related application in the catalytic oxidation of lean methane

Trivalent cerium (Ce3+) species has been recognized as the key active phase or promoter in many environmental applications. Here we report that the interfacial hybridization of TiO2 and CeO2 can favor the formation of Ce3+ species and further endow its supported palladium phase with excellent performance towards the elimination of lean methane at both dry and wet conditions. Systematic characterizations and designed experiments revealed that the interfacial hybridization between titania-rutile and deposited ceria species was critical for the enrichment of Ce3+ species, but the two facets exposed by commercial rutile, the (1 1 0) and the (1 1 1) facets, made different degrees of contributions. Combining XPS and XAS analysis with DFT calculations, we finally elucidated that, while the electrons of titanium in the rutile (1 1 0) system were effectively delivered to cerium and thus enhanced the formation of Ce3+ species, the (1 1 1) plane of rutile actually made minor contribution to the stabilization of trivalent cerium species. The facet-dependent titania-ceria interactions reported here may provide some inspirations for further design of ceria-based materials.

Process concepts and analysis for co-removing methane and carbon dioxide from the atmosphere

Methane is the second largest contributor to global warming after CO2, and it is hard to abate due to its low concentration in the emission sources and in the atmosphere. However, removing methane from the atmosphere will accelerate achieving net-zero targets, since its global warming potential is 28 over a 100-year period. This work presents first-of-its-kind process concepts for co-removal of methane and CO2 that combines the catalytic conversion of methane step (thermal/photo-catalytic) with CO2 capture. Proposed processes have been analyzed for streams with lean methane concentrations, which are non-fossil emissions originating in the agricultural sector or natural emissions from wetlands. If the proposed processes can overcome challenges in catalyst/material design to convert methane at low concentrations, they have the potential to remove more than 40% of anthropogenic and natural methane emissions from the atmosphere at a lower energy penalty than the state-of-the-art technologies for direct air capture of CO2.

Система совместного использования обедненного метана угольных пластов и биогаза для выработки электроэнергии в угольных шахтах

Purpose: Justification and development of new resource-saving technologies aimed at utilization of coal bed methane. The problem of low efficiency of utilization of lean methane-air mixtures is primarily due to the low content of methane itself, which varies significantly depending on the type of coal or concentration. This paper discusses the concept of a co-production system that mixes low-methane methane-air mixtures and biogas to generate power. Methods: Analysis of the possible volumes of utilized methane, biogas requirements and the suitability of the primary feedstock for co-generation of heat and electricity. Selection of appropriate parameters for the processes of utilization of mine methane. Analysis of the merits of the proposed method of utilization of lean coal mine methane. Results: It is recommended that biogas produced by agriculture and forestry in the vicinity of the mines be added to the dry methane stream to obtain the necessary gas concentration for electricity generation. Potential electricity production and greenhouse gas emission reductions have also been evaluated. The result shows that the co-production system can significantly improve the efficiency of poor methane-air mixtures in coal mines. Practical significance: The joint use of lean methane and biogas from straw offers practical advantages both economically, ensuring sufficient energy supply in mines, and as a foundation for broad future prospects. It allows for energy cost reduction and environmental pollution reduction, such as decreasing carbon dioxide emissions.