Search Results (132)

This work deals with the catalytic steam reforming of raw syngas to increase the efficiency of coupling gasification with downstream processes (such as fuel cells and catalytic chemical syntheses) by producing high-temperature, ready-to-use syngas without cooling it for cleaning and conditioning. Such a combination is considered a key point for the future exploitation of syngas produced by steam gasification of biogenic solid fuel. The design and construction of an integrated gasification and gas conditioning system were proposed approximately 20 years ago; however, they still require further in-depth study for practical applications. A 3D model of the freeboard of a pilot-scale, fluidized bed gasification plant equipped with catalytic ceramic candles was used to investigate the optimal operating conditions for in situ syngas upgrading. The global kinetic parameters for methane and tar reforming reactions were determined experimentally. A fluidized bed gasification reactor (~5 kWth) equipped with a 45 cm long segment of a fully commercial filter candle in its freeboard was used for a series of tests at different temperatures. Using a computational fluid dynamics (CFD) description, the relevant parameters for apparent kinetic equations were obtained in the frame of a first-order reaction model to describe the steam reforming of key tar species. As a further step, a CFD model of the freeboard of a 100 kWth gasification plant, equipped with six catalytic ceramic candles, was developed in ANSYS FLUENT^®. The composition of the syngas input into the gasifier freeboard was obtained from experimental results based on the pilot-scale plant. Simulations showed tar catalytic conversions of 80% for toluene and 41% for naphthalene, still insufficient compared to the threshold limits required for operating solid oxide fuel cells (SOFCs). An overly low freeboard temperature level was identified as the bottleneck for enhancing gas catalytic conversions, so further simulations were performed by injecting an auxiliary stream of O₂/steam (50/50 wt.%) through a series of nozzles at different heights. The best simulation results were obtained when the O₂/steam stream was fed entirely at the bottom of the freeboard, achieving temperatures high enough to achieve a tar content below the safe operating conditions for SOFCs, with minimal loss of hydrogen content or LHV in the fuel gas. Full article

The oxidative coupling of methane (OCM) is a promising process for converting methane directly into more valuable ethane and ethylene. In this work, high time resolution online mass spectrometry was employed to track the OCM reaction over a commercial La₂O₃ catalyst, focusing on the effects of methane to oxygen ratio, gas hourly space velocity (GHSV), and the presence of H₂O and CO in the feed gas on methane conversion and C₂ yield. The results demonstrated that an optimized GHSV (44,640 to 93,000 mL·g⁻¹·h⁻¹) and methane to oxygen ratio (CH₄/O₂ = 3) would achieve the highest methane conversion and C₂ yield at 740 °C. Furthermore, at a GHSV of 44,640 mL·g⁻¹·h⁻¹, the introduction of 1% H₂O into the reaction mixture resulted in a twofold increase in C₂ yield at 650 °C, while the addition of 1% CO led to a threefold increase in C₂ yield at 550 °C. A model in which only the front-end catalyst is active was also developed to show excellent agreement with the experimental data. The relationship between catalytic performance and the effective catalyst position in the catalyst bed provides important insights into optimizing reactor design and operating conditions to maximize C₂ yield and selectivity in the OCM reaction. Full article

This study focuses on optimizing C2 yields in the oxidative coupling of methane (OCM), a pivotal process for sustainable chemical production. By harnessing advanced machine learning (ML) techniques, this research aimed to predict C2 yields and identify the factors that drive catalytic performance. The Extra Trees Regressor emerged as the most effective model after a comprehensive evaluation across multiple datasets and methodologies. Key to the method was the use of an innovative Aggregated Catalyst Physicochemical Descriptor (ACPD) and stratified cross-validation, which effectively addressed feature complexity and target skewness. Hyperparameter optimization using Modified Sequential Model-Based Optimization (SMBO) further enhanced the model’s performance, achieving optimized R² values of 61.7%, 75.9%, and 92.0% for datasets A, B, and C, respectively, with corresponding reductions in the Mean Squared Error (MSE) and Root Mean Squared Error (RMSE). Additionally, SHAP (SHapley Additive exPlanations) analysis provided a detailed understanding of the model’s decision-making process, revealing the relative importance of individual features and their contributions to the predictive outcomes. This research not only achieved state-of-the-art predictive accuracy, but also deepened our understanding of the underlying chemical dynamics, offering practical guidance for catalyst design and operational optimization. These findings mark a significant advancement in catalysis, paving the way for future innovations in sustainable chemical manufacturing. Full article

Earth’s atmospheric methane (CH₄) concentration has risen more than 162% since pre-industrial levels in the mid-18th century, and about 30% of the rise in global temperatures since the pre-industrial era is due to CH₄ The build-up of methane in the atmosphere in 2020–2022 was the largest since systematic measurements started in 1983, more than double the average yearly growth rate measured over the previous 17 years (15.2 ppb yr⁻¹ vs. 5.71 ppb yr⁻¹, respectively). During 2020, with a growth rate of 14.81 ppb yr⁻¹, the level of atmospheric CH₄ broke the previous record (which was set in 1991), and it was broken again immediately the following year, with an increase of 17.64 ppb yr⁻¹ in 2021. For 2022, the final estimate is 13.25 ppb yr⁻¹, the fourth largest annual growth rate. The most recent explanations for this surge in tropospheric CH₄ include increased emissions from tropical wetlands, more floods, and increased temperatures. For 2020 and part of 2021, a reduction in the oxidative capacity of the atmosphere due to COVID-19 lockdowns was also proposed. Our main hypothesis is that this CH₄ surge in 2020–2021 may also be caused by reduced sulfate emissions, which have been shown to decrease methanotrophy and increase methanogenesis rates in wetlands. Then, for the CH₄ slowdown in 2022–2024, our hypotheses are that the emissions from wetlands remained high, but that there was an even higher increase in the oxidative capacity of the atmosphere due to multiple other parameters that are detailed in this article. This perspective review paper is mainly qualitative; it demonstrates that coupled climate–chemistry models will also need to integrate biochemistry, as the evolution of the atmospheric composition is multifactorial and non-linear. Full article

Chemical–structural characteristics of three differently synthesized research-benchmark Mn-Na-W-O_x/SiO₂ catalysts for the Oxidative Coupling of Methane (OCM) were systematically studied in this research. XRD, EDX, ICP-OES, and SEM/FIB-SEM techniques, as well as Carrier Gas Hot Extraction (CGHE) and high-temperature XRD analyses, were performed to explain the functional features of the studied catalysts, in particular, the features affecting the quantity and quality of the interactions of oxygen and methane with the catalyst surface and with other molecular and radical species. These enable tracking the potential for the oxygen activation and dynamic transformation of the solid-state chemistry on the surface and sub-surface of these Mn-Na-W-O_x/SiO₂ catalysts. These catalysts were synthesized, respectively, via the sol–gel synthesis method (Cat₁) and the incipient wetness impregnation of the non-structured silica support (Cat₂) and structured SBA-15 silica support (Cat₃), under different sets of temperatures and gas compositions. The catalysts with the homogenous distribution of active components, namely Cat₁ and Cat₃, showed similar trends in terms of their dynamic interaction with oxygen species. They also showed higher levels of crystallinity of the active materials and higher catalytic selectivity towards ethane and ethylene. An explanation is given as to how the structural characteristics of the catalysts on the nanometer–micrometer scale contribute to these. The gained knowledge will be crucial in the selection and treatment of the support and developing a proper synthesis approach for the ultimate goal of designing a selective OCM catalyst. Full article

The Okinawa Trough (OT) has been a focus of scientific research for many years due to the presence of vibrant hydrothermal and cold seep activity within its narrow basin. However, the spatial distribution and environmental drivers of microbial communities in OT sediments remain poorly understood. The present study aims to address this knowledge gap by investigating microbial diversity and abundance at ten different sampling sites in a transitional zone between hydrothermal vents and cold seeps in the OT. The microbial community at two sampling sites (G08 and G09) in close proximity to hydrothermal vents showed a high degree of similarity. However, lower bacterial and archaeal abundances were found in these sites. The archaeal groups, classified as Hydrothermarchaeota and Thermoplasmata, showed a comparatively higher relative abundance at these sites. In addition, ammonia-oxidizing archaea (AOA), from the family Nitrosopumilaceae, were found to have a higher relative abundance in the OT surface sediments at sampling sites G03, G04, G05, G06, and G07. This result suggests that ammonia oxidation may be actively occurring in these areas. Furthermore, Methylomirabilaceae, which are responsible for methane oxidation coupled with nitrite reduction, dominated three sampling sites (G07, G08, and G09), implying that N-DAMO may play an important role in mitigating methane emissions. Using the FAPROTAX database, we found that predicted prokaryotic microbial functional groups involved in methyl-reducing methanogenesis and hydrogenotrophic methanogenesis were most abundant at sites G08 and G09. At sampling sites G01 and G02, functional groups such as hydrocarbon degradation, methanotrophy, methanol oxidation, denitrification, sulfate respiration, and sulfur oxidation were more abundant. Nitrogen content is the most important environmental factor determining the bacterial and archaeal communities in the OT surface sediments. These results expand our knowledge of the spatial distribution of microbial communities in the transitional zone between hydrothermal vents and cold seeps in the OT. Full article

The global production of brewers’ spent grains (BSG) is 37 million tons yearly. Composting represents an eco-friendly method to manage and valorize organic by-products in a circular economy model. This project aims to compare two BSG bin-composting mixtures (BSG and wheat straw with pig slurry solid fraction, MIX1, or sheep manure, MIX2) and approaches (manual turning, MT, and static composting, ST). The two mixtures’ physicochemical characteristics and greenhouse gas (GHG) emissions were assessed during the process. The evolution of physicochemical properties is reported in detail. Headspace samples of GHG emissions were collected and analyzed with gas chromatography coupled with specific detectors. Carbon dioxide (CO₂) emissions were 34.3 ± 0.03 and 31.0 ± 0.06 g C kg⁻¹ fresh matter (FM) for MIX1-MT and MIX2-MT, and 28.8 ± 0.01 and 31.2 ± 0.02 g Ckg⁻¹ FM for MIX1-ST and MIX2-ST. Methane emissions were negligible (all conditions < 0.086 ± 0.00 mg C kg⁻¹ FM). Nitrous oxide (N₂O) emissions from composting are affected by the substrate, bulking material, pile dimension, and manure. Particularly, the total emissions of N₂O, estimated as CO₂ equivalents, were 45.8 ± 0.2 and 63.0 ± 0.4 g CO₂ eq kg⁻¹ FM for MIX1-MT and MIX1-ST, respectively. In both composting approaches, MIX2 showed a low CO₂ equivalent (1.8 ± 0.02 and 9.9 ± 0.05 g CO₂ eq kg⁻¹ FM for MT and ST), likely due to incomplete decomposition. The bin-composting process represents a solution for recycling and reusing organic waste and livestock manure in small to medium-sized breweries. The solid fraction of the pig slurry resulted in the most suitable manure. Full article

Terrestrial Storage of Biomass (TSB) is a Negative Emission Technology for removing CO₂ already in the atmosphere. TSB is compared to other NETs and is shown to be a natural, carbon-efficient, and low-cost option. Nature performs the work of removal by growing biomass via photosynthesis. The key to permanent sequestration is to bury the biomass in pits designed to minimize the decomposition. The chemistry of biomass formation and decomposition is reviewed to provide best practices for the TSB burial pit design. Methane formation from even a small amount of decomposition has been raised as a concern. This concern is shown to be unfounded due to a great difference in time constants for methane formation and its removal from the air by ozone oxidation. Methane has a short lifetime in air of only about 12 years. Woody biomass decomposition undergoes exponential decay spread over hundreds to thousands of years. It is inherently slow due to the cross-linking and dense packing of cellulose, which means that the attack can only occur at the surface. A model that couples the slow and exponential decay of the rate of methane formation with the fast removal by oxidation shows that methane will peak at a very small fraction of the buried biomass carbon within about 10 years and then rapidly decline towards zero. The implication is that no additional equipment needs to be added to TSB to collect and burn the methane. Certified carbon credits are listed on various exchanges. The US DOE has recently issued grants for TSB development. Full article

The photocatalytic oxidative coupling of methane (OCM) on metal-loaded one-dimensional TiO₂ nanowires (TiO₂ NWs) was performed. With metal loading, the electric and optical properties of TiO₂ NWs were adjusted, contributing to the improvement of the activity and selectivity of the OCM reaction. In the photocatalytic OCM reaction, the 1.0 Au/TiO₂ NW catalyst exhibits an outstanding C₂H₆ production rate (4901 μmol g⁻¹ h⁻¹) and selectivity (70%), alongside the minor production of C₃H₈ and C₂H₄, achieving a total C₂–C₃ hydrocarbon selectivity of 75%. In contrast, catalysts loaded with Ag, Pd, and Pt show significantly lower activity, with Pt/TiO₂ NWs producing only CO₂, indicating a propensity for the deep oxidation of methane. The O₂-TPD analyses reveal that Au facilitates mild O₂ adsorption and activation, whereas Pt triggers excessive oxidation. Spectroscopic and kinetic studies demonstrate that Au loading not only enhances the separation efficiency of photogenerated electron–hole pairs, but also promotes the generation of active oxygen species in moderate amounts, which facilitates the formation of methyl radicals and their coupling into C₂H₆ while suppressing over-oxidation to CO₂. This work provides novel insights and design strategies for developing efficient photocatalysts. Full article

The fusion of catalytic and electronic properties, coupled with empirical data, provides enriched perspectives into catalyst evaluation and design, thus propelling advancement and innovation in the domain of heterogeneous catalytic reactions, including the oxidative coupling of methane (OCM) reaction. Comparative assessment of various machine learning methodologies on OCM reaction datasets reveals that the Random Forest regression (RFR) model excels in C₂H₄ and C₂H₆ combined yield (C₂y) predictive accuracy, boasting an average R² value of 0.98. The hierarchy of modeling performance stands as follows: RFR > XGBR > SVR > DNN. The MSE and MAE metrics of the RFR models were observed to be lower compared to alternative models, ranging from 0.12 to 9.03 for MSE and 0.21 to 2.02 for MAE. Model accuracy follows the order of C₂H₆y > C₂H₄y > C₂y > CO₂y > CH₄_conv (methane conversion). When examining the influence of model features, C₂y increases proportionally with an augmentation in dataset attributes, including the quantity of alkali/alkali-earth metal moles in the catalyst (13.69%), the atomic number (6.24%) of the catalyst promoter, and the Fermi energy of the metal, with a less pronounced impact compared to the case of temperature (33.70%). This suggests a highly nonlinear correlation between combined ethylene and ethane yield and temperature. Other factors, such as the bandgap of the active metal oxide and the support, as well as the Fermi energy of the catalyst support, were observed to have a relatively modest effect on the predictive models for combined ethylene and ethane yield and methane conversion. Full article

To date, only a few microbial community studies of cold seeps at the South China Sea (SCS) have been reported. The cold seep dominated by tubeworms was discovered at South Yungan East Ridge (SYER) offshore southwestern Taiwan by miniROV. The tubeworms were identified and proposed as Paraescarpia formosa sp. nov. through morphological and phylogenetic analyses. The endosymbionts in the trunk of P. formosa analyzed by a 16S rRNA gene clone library represented only one phylotype, which belonged to the family Sedimenticolaceae in Gammaproteobacteria. In addition, the archaeal and bacterial communities in the habitat of tubeworm P. formosa were investigated by using high-phylogenetic-resolution full-length 16S rRNA gene amplicon sequencing. The results showed that anerobic methane-oxidizing archaea (ANME)-1b was most abundant and ANME-2ab was minor in a consortia of the anerobic oxidation of methane (AOM). The known sulfate-reducing bacteria (SRB) partners in AOM consortia, such as SEEP-SRB1, -SRB2, and -SRB4, Desulfococcus and Desulfobulbus, occurred in a small population (0–5.7%) at the SYER cold seep, and it was suggested that ANME-1b and ANME-2ab might be coupled with multiple SRB in AOM consortia. Besides AOM consortia, various methanogenic archaea, including Bathyarchaeota (Subgroup-8), Methanocellales, Methanomicrobiales, Methanosarcinales, Methanofastidiosales and Methanomassiliicoccales, were identified, and sulfur-oxidizing bacteria Sulfurovum and Sulfurimonas in phylum Epsilonbacteraeota were dominant. This study revealed the first investigation of microbiota in and around tubeworm P. formosa discovered at the SYER cold seep offshore southwestern Taiwan. We could gain insights into the chemosynthetic communities in the deep sea, especially regarding the cold seep ecosystems at the SCS. Full article

Chemical looping partial oxidation of methane (CLPOM) is a low energy consumption and environmentally friendly new technology that can generate syngas. The main challenge is to find suitable oxygen carriers, which should be highly active, stable, low cost, and eco-friendly. This study found that Fe₂SiO₄ had good reactivity in the CLPOM process. Thermodynamic calculations were carried out by FactSage8.1 to demonstrate the feasibility of Fe₂SiO₄ as an oxygen carrier for CLPOM. Fe₂SiO₄ was prepared by the direct ball milling method and the high-temperature solid-phase synthesis method. The reaction properties of Fe₂SiO₄ were investigated in the fixed bed reactor. The XRD and FTIR results indicate that Fe₂SiO₄ can be synthesized successfully through the high-temperature solid-phase synthesis method. The results of fixed bed experiments showed that when the reaction temperature was 980 °C and the reaction time was 28 min, the $X_{C{H}_4}$ reached 87%, and the $S_{H_2}$ and $S_{\mathit{CO}}$ were 70% and 71%, respectively. Subsequently, 20 redox cycle experiments were conducted under the optimal reaction conditions. The results showed that Fe₂SiO₄ exhibited good reactivity in the first two cycles, and as the reaction progressed, the reduced oxygen carrier could not regain the lattice oxygen, leading to a decline in cyclic performance. This study demonstrates that Fe₂SiO₄ can couple CO₂ and CH₄ to produce syngas and is conducive to reducing carbon emissions. Full article

Iron monosulfides and neoformed pyrite below the sulfate–methane transition zone (SMTZ) of rapidly accumulating turbiditic sediments from the Gaoping submarine canyon off southwestern Taiwan were examined by SEM-EDS-EBSD, HRTEM, and HAADF STEM to investigate their microstructural characteristics and processes of formation and transformation. Within a few meters below the SMTZ, mackinawite (Mkw) is largely replaced by interlayered greigite-pyrrhotite (Grg-Po) with {111}_Grg//{001}_Po and ⟨110⟩_Grg//⟨110⟩_Po, followed by pyrite neoformation in clusters of disseminated matrix grains consisting of coalescing pyrite microcrystals, arrays of polycrystalline interlayer pyrite grains between the cleavage planes of layer silicates, with each grain’s core having inclusions of interlayered Grg-Po locally containing relict Mkw, and amassed pyrite microcrystals on the surface of porous interlayered Grg-Po micronodules. In the deeper sediments, neoformed pyrite is absent and Mkw is largely preserved, with partial replacement by interlayered Grg-Po having an overall topotactic relationship of ⟨110⟩_Grg//⟨110 ⟩_Po//⟨100⟩_Mkw and {111}_Grg//(001)_Po//~{011}_Mkw and a sharp reaction front without transitional profiles. The mineral grain boundaries and structural discontinuities with Mkw resulting from extensive interlayering between Grg {111} cubic close-packed segments and Po {001} hexagonal close-packed layers could serve as conduits for fluid flow and mass transport to drive the replacement reaction. The conversion of Mkw to metastable interlayered Grg-Po is inferred to occur through interface-coupled dissolution–reprecipitation processes associated with partial oxidation while the partial replacement of interlayered Grg-Po ± minor relict Mkw by pyrite microcrystals with irregular grain boundaries and orientations probably occurred via a dissolution–precipitation mechanism. Mkw could be initially formed by sulfate reduction driven by anaerobic oxidation of methane in reactive iron-rich sediments in paleo-SMTZs and subsequently transformed into interlayered Grg-Po followed by pyrite neoformation in the sulfidization front below the SMTZ or recent SMTZs in the Gaoping submarine canyon sediments. Full article

The combination of electronic and catalytic features, in conjunction with empirical investigation, provides enriched perspectives on the analysis of catalysts, thus propelling progress and design. This study employs computational methods to deduce electronic characteristics, including properties such as bandgap, Fermi energy, and magnetic moment, for known catalysts involved in the oxidative coupling of methane (OCM) reaction. Through the comparison of these attributes with existing experimental OCM data, the ability to forecast the effectiveness of catalysis and subsequent reaction results is achieved, spanning CH₄, C₂H₄, C₂H₆, and CO₂ production. Transition metals, including Pt, Rh, Ru, and Ir, turn out to be promising catalyst promoters of OCM reactions. This study identified 58 innovative blends of metallic oxides and 3480 new catalytic configurations specifically designed for methane conversion at a moderately low temperature of 700 °C, placing them as effective catalysts for the OCM reaction. These emerging catalysts are projected to result in a rise in methane conversion extending from ±38.5% to ±95%, presenting a significant increase from the upper limit methane conversion of 36% reported in previous investigations. Full article

Autothermal oxidative coupling of methane (OCM) is a highly attractive approach for methane utilization. If platinum-based catalysts are operated in short-contact-time reactors with high space velocities, high methane conversion can be achieved. Using a 1 wt.% Pt/Al₂O₃ catalyst as a benchmark, the present study elucidates how different dopants, namely Ni, Sn, and V₂O₅, affect the OCM reaction. Kinetic catalyst tests reveal that acetylene (C₂H₂) is the predominant C₂ product, irrespective of the catalyst formulation or operation conditions. Furthermore, the use of bimetallic catalysts allows either for the maintenance or even the improvement of the C₂ selectivity during OCM, which is attributed to synergistic effects that occur when expensive Pt is partially replaced by cheaper dopants. In particular, the 1 wt.% Pt/Al₂O₃ reference catalyst yielded a maximum C₂ selectivity of 8.2%, whereas the best-performing doped sample 0.25 wt.% Pt 0.75 wt.% V₂O₅/Al₂O₃ yielded a total C₂ selectivity of 11.3%. Full article