Methane, Volume 2, Issue 4 (December 2023) – 8 articles

In this research, we investigate the impact of Li doping on a TiO₂ support, synthesized through the sol-gel method, with a focus on varying the aging time. Our objective is to elucidate how aging duration and doping influence the surface basicity, thereby mitigating carbon formation and amplifying the catalytic efficacy of Ni-loaded catalysts (15 wt.%). Essential characterization techniques encompass X-ray diffraction, H₂-TPR, FE-SEM, N₂-physisorption, DLS, FTIR, and Raman spectroscopies. Our findings reveal that extended aging periods promote the development of a basic character, attributable to oxygen defects within TiO₂. This inherent trait bears significant implications for catalyst performance, stability, and carbon formation during the reaction. Remarkably, the catalyst with the highest catalytic activity and stability boasts an 85% relative basicity, a property also induced by incorporating lithium into the TiO₂ support. Full article

Ground- and drone-based surface emission monitoring (SEM) campaigns were performed at two municipal solid waste landfills, during the same week as mobile tracer correlation method (TCM) testing was used to measure the total methane emissions from the same landfills. The G-SEM and the D-SEM data, along with wind data, were used as input into an inverse modeling approach combined with an optimization-based methane emission estimation method (implemented in a tool called SEM2Flux). This approach involves the use of backward dispersion modeling to estimate the whole-site methane emissions from a given landfill and the identification of locations and emission rates of major leaks. SEM2Flux is designed to exploit the measured surface methane concentration concurrently with wind data and tackle two problems: (1) inferring the estimates of methane rates from individual landfills, and (2) identifying the likely locations of the main emission sources. SEM2Flux results were also compared with emission estimates obtained using TCM. In Landfill B, the average TCM-measured methane emissions was 1178 Kg/h, with a standard deviation of 271 Kg/h. In Landfill C, the average TCM-measured emission rate was 601 Kg/h, with a standard deviation of 292 Kg/h. For both landfills, the D-SEM data yielded statistically similar estimates of methane emissions as the TCM-measured emissions. On the other hand, the G-SEM data yielded comparable estimates of emissions to TCM-measured emissions only for Landfill C, where the D-SEM and G-SEM data were statistically not different. The results of this study showcase the ability of this method using surface concentrations to provide a rapid and simple estimation of fugitive methane emissions from landfills. Such an approach can also be used to assess the effectiveness of different remedial actions in reducing fugitive methane emissions from a given landfill. Full article

Anaerobic digestion (AD) of residues from integrated first- and second-generation ethanol (1G2G) biorefineries is a sustainable method for energy recovery through biogas production. This study evaluated the co-digestion of 1G vinasse, 2G vinasse and pentose liquor (from the pretreatment of sugarcane bagasse for 2G ethanol production) compared to individual digestions using biochemical methane potential (BMP) assays. The results showed some “key” micronutrients from the substrates that affected methane (CH₄) production, while their balance provided by co-digestion achieved high digestibility (95%). High iron (Fe) and nickel (Ni) concentrations, in addition to furfural (0.33 g L⁻¹) in pentose liquor seemed to decrease its CH₄ production potential. Despite these adverse effects observed in mono-digestion, co-digestion was beneficial for this substrate, increasing digestibility (52%) and BMP (118%). The highest BMP was observed in vinasse 2G (631 ± 6 NmL CH₄ gTVS⁻¹), with no significant difference compared to the adjusted modified Gompertz model (624 ± 10 NmL CH₄ gTVS⁻¹). The co-digestion system also presented the highest specific CH₄ production rate (20 ± 1 NmL CH₄ gTVS⁻¹day⁻¹) and shortened the lag phase by 19% compared to the AD of isolated 1G vinasse with the second lowest BMP value (494 ± 11 NmL CH₄ gTVS⁻¹). Full article

Chemical Vapor Infiltration (CVI) has proven remarkably successful in producing strong and lightweight ceramic matrix composite materials. This technology has matured to regular industrial use. However, two fundamental problems remain, and those are the formation of pores and depositing of weaker material than silicon carbide ($SiC$), namely, Si. Definitive knowledge of the molecular mechanism would catalyze an advance in the chemical precursors used in CVI. In this work, the CVI reaction is modeled using density functional theory (DFT) calculations. The DFT calculations here use the Bayesian Error Estimation Functional with van der Waals correction (BEEF-vdW). The main findings begin with C deposition determining the rate of solid $SiC$ growth due to Si being far more reactive. Therefore, increasing the C content of the precursor is a logical CVI strategy. Methane ($C{H}_4$) is more reactive than ethane ($C_2{H}_6$) and ethylene ($C_2{H}_2$) and would be effective as an additive to the chemical precursor. Increasing the deposition rate of C has the benefit of decreasing pure Si deposits. Si melts at 1410 °C and CMCs are used in high-temperature settings beyond this melting point, including in aeroengines and nuclear fuel cladding. Full article

Driven by increasing greenhouse gas (GHG) concentrations in the atmosphere, extreme weather events have become more frequent and their impacts on human lives have become more severe. Therefore, the need for short-term GHG mitigations is urgent. Recently, methane has been recognized as an important mitigation target due to its high global warming potential (GWP). However, methane’s low concentration in the atmosphere and stable molecular structure make its removal from the air highly challenging. This review first discusses the fundamental aspects of the challenges in atmospheric methane removal and then briefly reviews the existing research strategies following the mechanisms of natural methane sinks. Although still in its infancy, recent research on methane removal from the air holds great potential for slowing down global warming. At the same time, it is important to carefully examine the energy consumption of these methane removal strategies and whether they will be able to achieve net GHG reduction. In addition, due to the scale of methane removal from the air, any potential solution’s environmental impacts must be carefully evaluated before it can be implemented in practice. Full article

In this paper, we analyze the autothermal reforming (ATR) of methane through Gibbs energy minimization and entropy maximization methods to analyze isothermic and adiabatic systems, respectively. The software GAMS^® 23.9 and the CONOPT3 solver were used to conduct the simulations and thermodynamic analyses in order to determine the equilibrium compositions and equilibrium temperatures of this system. Simulations were performed covering different pressures in the range of 1 to 10 atm, temperatures between 873 and 1073 K, steam/methane ratio was varied in the range of 1.0/1.0 and 2.0/1.0 and oxygen/methane ratios in the feed stream, in the range of 0.5/1.0 to 2.0/1.0. The effect of using pure oxygen or air as oxidizer agent to perform the reaction was also studied. The simulations were carried out in order to maintain the same molar proportions of oxygen as in the simulated cases considering pure oxygen in the reactor feed. The results showed that the formation of hydrogen and synthesis gas increased with temperature, average composition of 71.9% and 56.0% using air and O₂, respectively. These results are observed at low molar oxygen ratios (O₂/CH₄ = 0.5) in the feed. Higher pressures reduced the production of hydrogen and synthesis gas produced during ATR of methane. In general, reductions on the order of 19.7% using O₂ and 14.0% using air were observed. It was also verified that the process has autothermicity in all conditions tested and the use of air in relation to pure oxygen favored the compounds of interest, mainly in conditions of higher pressure (10 atm). The mean reductions with increasing temperature in the percentage increase of H₂ and syngas using air under 1.5 and 10 atm, at the different O₂/CH₄ ratios, were 5.3%, 13.8% and 16.5%, respectively. In the same order, these values with the increase of oxygen were 3.6%, 6.4% and 9.1%. The better conditions for the reaction include high temperatures, low pressures and low O₂/CH₄ ratios, a region in which there is no swelling in terms of the oxygen source used. In addition, with the introduction of air, the final temperature of the system was reduced by 5%, which can help to reduce the negative impacts of high temperatures in reactors during ATR reactions. Full article

The relaxation processes induced by exposure of the Ar matrices doped with CH₄ (0.1–10%) to an electron beam were studied with a focus on the dynamics of radiolysis products—H atoms, H₂ molecules, CH radicals, and energy transfer processes. Three channels of energy transfer to dopant and radiolysis products were discussed, including free charge carriers, free excitons and photons from the “intrinsic source” provided by the emission of the self-trapped excitons. Radiolysis products along with the total yield of desorbing particles were monitored in a correlated manner. Analysis of methane transformation reactions induced by free excitons showed that the CH radical can be considered a marker of the CH₃ species. The competition between exciton self-trapping and energy transfer to the dopant and radiolysis products has been demonstrated. A nonlinear concentration behavior of the H atoms in doped Ar matrices has been established. Real-time correlated monitoring of optical emissions (H atom and CH₃ radicals), particle ejection, and temperature revealed a nonmonotonic behavior of optical yields with a strong luminescence flash after almost an hour of exposure, which correlated with the explosive pulse of particle ejection and temperature. The connection of this phenomenon with the processes of energy transfer and recombination reactions has been established. It is shown that the delayed explosive ejection of particles is driven by both the recombination of H atoms and CH₃ radicals. This occurs after their accumulation to a critical concentration in matrices at a CH₄ content C ≥ 1%. Full article

Rice fields are one of the important anthropogenic sources of methane emissions. Methanotrophs dwelling near the rice roots and at the oxic–anoxic interface of paddy fields can oxidize a large fraction of the generated methane and are therefore considered to be important. Nitrogen fixation in rice root-associated methanotrophs is well known. Our aim in this study was to explore the potential of methanotrophs as bio-inoculants for rice and the studies were performed in pot experiments in monsoon. Ten indigenously isolated methanotrophs were used belonging to eight diverse genera of Type Ia, Type Ib, and Type II methanotrophs, including the newly described genera and/or species, Methylocucumis oryzae and Methylolobus aquaticus, as well as Ca. Methylobacter oryzae and Ca. Methylobacter coli. Additionally, two consortia (Methylomonas strains and Methylocystis-Methylosinus strains) were used. Nitrogen fixation pathways or nifH genes were detected in all of the used methanotrophs. Plant growth promotion (PGPR) was seen in terms of increased plant height and grain yield. Nine out of twelve (seven single strains and two consortia) showed positive effects on grain yield (6–38%). The highest increase in grain yield was seen after inoculation with Ca. Methylobacter coli (38%) followed by Methylomonas consortium (35%) and Methylocucumis oryzae (31%). Methylomagnum ishizawai inoculated plants showed the highest plant height. Methylocucumis oryzae inoculated plants showed early flowering, grain formation, and grain maturation (~17–18 days earlier). In all the pot experiments, minimal quantities of nitrogen fertilizer were used with no additional organic fertilizer inputs. The present study demonstrated the possibility of developing methanotrophs as bio-inoculants for rice agriculture, which would promote plant growth under low inputs of nitrogenous fertilizers. Although the effect of methanotrophs on methane mitigation is still under investigation, their application to reduce methane emissions from rice fields could be an added advantage. Full article