Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits ...Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.展开更多
The objective of this study is to propose an optimal plant design for blue hydrogen production aboard a liquefiednatural gas(LNG)carrier.This investigation focuses on integrating two distinct processes—steam methaner...The objective of this study is to propose an optimal plant design for blue hydrogen production aboard a liquefiednatural gas(LNG)carrier.This investigation focuses on integrating two distinct processes—steam methanereforming(SMR)and ship-based carbon capture(SBCC).The first refers to the common practice used to obtainhydrogen from methane(often derived from natural gas),where steam reacts with methane to produce hydrogenand carbon dioxide(CO_(2)).The second refers to capturing the CO_(2) generated during the SMR process on boardships.By capturing and storing the carbon emissions,the process significantly reduces its environmental impact,making the hydrogen production“blue,”as opposed to“grey”(which involves CO_(2) emissions without capture).For the SMR process,the analysis reveals that increasing the reformer temperature enhances both the processperformance and CO_(2) emissions.Conversely,a higher steam-to-carbon(s/c)ratio reduces hydrogen yield,therebydecreasing thermal efficiency.The study also shows that preheating the air and boil-off gas(BOG)before theyenter the combustion chamber boosts overall efficiency and curtails CO_(2) emissions.In the SBCC process,puremonoethanolamine(MEA)is employed to capture the CO_(2) generated by the exhaust gases from the SMR process.The results indicate that with a 90%CO_(2) capture rate,the associated heat consumption amounts to 4.6 MJ perkilogram of CO_(2) captured.This combined approach offers a viable pathway to produce blue hydrogen on LNGcarriers while significantly reducing the carbon footprint.展开更多
Background The enteric methane inhibitor 3-nitrooxypropanol(3-NOP)inhibits the key enzyme in ruminal methanogenesis,but whether short-term(ST)and long-term(LT)dietary supplementation has similar effects on rumen micro...Background The enteric methane inhibitor 3-nitrooxypropanol(3-NOP)inhibits the key enzyme in ruminal methanogenesis,but whether short-term(ST)and long-term(LT)dietary supplementation has similar effects on rumen microbiota in beef cattle and how microbes change after 3-NOP withdrawal have not been studied.This study investigated changes in rumen bacteria,archaea,and protozoa after ST and LT dietary supplementation and removal of 3-NOP using metataxonomic analysis.Results A total of 143 rumen samples were collected from two beef cattle studies with 3-NOP supplementation.The ST study(95 samples)used eight ruminally cannulated beef cattle in a 4×4 Latin square design with four 28-d of 3-NOP treatments[mg/kg of dry matter(DM)]:control:0,low:53,med:161,and high:345.The LT study(48 samples)was a completely randomized design with two 3-NOP treatments[control:0,and high:280 mg/kg of DM)fed for 112-d followed by a 16-d withdrawal(without 3-NOP).Bacterial and archaeal communities were significantly affected by 3-NOP supplementation but limited effects on protozoal communities were observed.Under ST supplementation,the relative abundances of Prevotella,Methanobrevibacter(Mbb.)ruminantium,Methanosphaera sp.ISO3-F5,and Entodinium were increased(Q<0.05),whereas those of Mbb.gottschalkii and Epidinium were decreased(Q<0.05)with 3-NOP supplementation.In LT study,relative abundances of Mbb.ruminantium,and Methanosphaera sp.Group5 were increased(Q<0.05),while those of Saccharofermentans and Mbb.gottschalkii were decreased(Q<0.05)with 3-NOP supplementation.Comparison between 3-NOP supplementation and the withdrawal revealed increased relative abundances of Clostridia UCG-014 and Oscillospiraceae NK4A214 group and decreased those of Eubacterium nodatum group and Methanosphaera sp.Group5(P<0.05)after 3-NOP withdrawal.Further comparison of rumen microbiota between control and 3-NOP withdrawal showed significantly higher(P=0.029)relative abundances of Eggerthellaceae DNF00809,p-1088-a5 gut group,and Family XII UCG-001 in control group while no significant differences were detected for archaea and protozoa.Microbial network analysis revealed that microbial interactions differed by both 3-NOP dose and durations.Conclusions Both ST and LT supplementation affected overall rumen microbial profile,with individual microbial groups responded to 3-NOP supplementation differently.After 3-NOP withdrawal,not all microbes showed recovery,indicating that the 3-NOP driven shifts were only partially reversible.These findings provide an understanding of the effects of 3-NOP on rumen microbial communities and their adaptability to methane mitigation strategies.展开更多
In the development of coalbed methane(CBM)reservoirs using multistage fractured horizontal wells,there often exist areas that are either repeatedly stimulated or completely unstimulated between fracturing stages,leadi...In the development of coalbed methane(CBM)reservoirs using multistage fractured horizontal wells,there often exist areas that are either repeatedly stimulated or completely unstimulated between fracturing stages,leading to suboptimal reservoir performance.Currently,there is no well-established method for accurately evaluating the effectiveness of such stimulation.This study introduces,for the first time,the concept of the Fracture Network Bridging Coefficient(FNBC)as a novel metric to assess stimulation performance.By quantitatively coupling the proportions of unstimulated and overstimulated volumes,the FNBC effectively characterizes the connectivity and efficiency of the fracture network.A background grid calibration method is developed to quantify the stage-controlled volume,effectively stimulated volume,unstimulated volume,and repeatedly stimulated volume among different stages of horizontal wells.Furthermore,an optimization model is constructed by taking the FNBC as the objective function and the fracturing injection rate and fluid volume as optimization variables.The Simultaneous Perturbation Stochastic Approximation(SPSA)algorithm is employed to iteratively perturb and optimize these variables,progressively improving the FNBC until the optimal displacement rate and fluid volume corresponding to the maximum FNBC are obtained.Field application in a typical CBM multistage fractured horizontal well in China demonstrates that the FNBC increased from 0.358 to 0.539(a 50.6% improvement),with the injection rate rising from 16 m^(3)/min to 24 m^(3)/min and the average fluid volume per stage increasing from 2490 m^(3) to 3192 m^(3),significantly enhancing the stimulation effectiveness.This research provides theoretical support for designing high-efficiency stimulation strategies in unconventional reservoirs under dynamic limits.展开更多
Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH_(4) is summarized.The influen...Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH_(4) is summarized.The influence of additives and surface modification methods on improving their catalytic performance is discussed as is the reaction mechanism,especially the structurefunction relationship produced by the carbon.The review provides a comprehensive directory for the rational design of carbon-supported Ni-based catalysts for the methanation of CO_(2).展开更多
Significant differences exist between deep and medium-shallow coalbed methane(CBM)reservoirs.The unclear understanding of flowback and production behavior severely constrains the development of deep CBM resources.To a...Significant differences exist between deep and medium-shallow coalbed methane(CBM)reservoirs.The unclear understanding of flowback and production behavior severely constrains the development of deep CBM resources.To address this challenge,guided by the gas-liquid two-phase flow theory in ultra-low permeability reservoirs,and integrating theoretical analysis,numerical simulation,and insights from production practices,this study classifies the flowback and production stages of deep CBM well considering the Daning-Jixian Block,Eastern Ordos Basin as a representative case.We summarize the flowback characteristics for each stage and establish a standard flowback production type curve,aiming to guide field operations.The results indicate that:(a)The production process of deep CBM horizontal wells can be divided into five distinct stages:initial single-phase water dewatering stage,initial gas appearance to peak water production stage,gas breakthrough to peak gas production stage,stable production and decline stage,and low-rate production stage.(b)Based on reservoir energy,two standard type curves for horizontal well flowback production are established:the‘Sufficient Reservoir Energy’type and the‘Insufficient Reservoir Energy’type.The former achieves a higher initial gas rate(up to 12×10^(4)m^(3)/d)but exhibits poorer stability,while the latter achieves a lower stable rate(up to 8×10^(4)m^(3)/d)but demonstrates stronger stability.Numerical simulation confirms these behavioral patterns and reveals the underlying mechanisms related to the effectively drained area where pressure is significantly depleted.The findings from this study have guided the flowback production operations in 53 deep CBM wells with positive results,demonstrating high potential for broad application.展开更多
Background Methane(CH_(4))emissions from ruminants significantly contribute to greenhouse gas effects and energy loss in livestock production.Methyl-coenzyme M reductase(MCR)is the key enzyme in methanogenesis,making ...Background Methane(CH_(4))emissions from ruminants significantly contribute to greenhouse gas effects and energy loss in livestock production.Methyl-coenzyme M reductase(MCR)is the key enzyme in methanogenesis,making it a promising target for CH_(4) mitigation.This study aimed to identify and validate plant-derived inhibitors by using molecular docking to screen compounds with strong binding affinity to the F430 active site of MCR and assessing their efficacy in reducing CH_(4) emissions.Results Molecular docking analysis identified salvianolic acid C(SAC)as a potent inhibitor of MCR,showing a strong binding affinity to the F430 active site(binding energy:-8.2 kcal/mol).Enzymatic inhibition assays confirmed its inhibitory effect,with a half-maximal inhibitory concentration(IC50)of 692.3μmol/L.In vitro rumen fermentation experiments demonstrated that SAC supplementation(1.5 mg/g DM)significantly reduced CH_(4)production(P<0.01)without negatively affecting major fermentation parameters.Microbial community analysis using 16S rRNA sequencing and metagenomics revealed that SAC selectively altered the rumen microbiota,increasing the relative abundance of Bacteroidota while significantly reducing Methanobrevibacter(P=0.04).Moreover,metagenomic analysis showed the downregulation of key methanogenesis-related genes(mcrA and rnfC),suggesting a dual mechanism involving direct enzymatic inhibition and microbial community modulation.Conclusions These findings indicate that SAC effectively reduces CH_(4)production by inhibiting MCR activity and reshaping the rumen microbial community.As a plant-derived compound with strong inhibitory effects on methanogenesis,SAC presents a promising and sustainable alternative to synthetic CH_(4) inhibitors,offering potential applications for mitigating CH_(4)emissions in livestock production.展开更多
The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environ...The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.展开更多
With the maturation of coalbed methane(CBM)exploitation and the transition into the late stages of dewatering and gas production,liquid loading in gathering pipelines has emerged as a major constraint on productivity ...With the maturation of coalbed methane(CBM)exploitation and the transition into the late stages of dewatering and gas production,liquid loading in gathering pipelines has emerged as a major constraint on productivity and operational stability.Based on real-time field data and gas-liquid physicochemical analyses,this study elucidates the mechanisms governing liquid loading formation under varying temperature,pressure,and water saturation conditions.An HYSYS model is employed to determine the water dew point,while the Turner model is used to evaluate the critical conditions for liquid holdup.The results indicate that gas water saturation exerts the dominant influence on liquid loading risk,followed by pressure,whereas temperature plays a comparatively minor role.When water saturation exceeds 2%and the operating temperature falls below the dew point,condensation-driven liquid loading increases sharply.To further characterize the spatial distribution of liquid accumulation,a steady-state OLGA model of a DN100 gathering pipeline network is developed to examine the effects of pipe diameter,water saturation,and soil temperature.The simulations show that larger pipe diameters and higher water saturation significantly aggravate liquid holdup,while elevated soil temperature mitigates liquid accumulation.Moreover,the liquid holdup ratio is found to correlate closely with flow regime transitions,confirming its suitability as a key indicator of liquid loading risk.Based on these findings,optimization strategies for pipeline design and operation are proposed.To mitigate liquid loading,the gathering pipeline velocity should be maintained above the critical value of 1.63 m/s,and the gas water content should be strictly controlled below 2%.Under operating conditions representative of the Hancheng block,it is recommended to reduce the pipeline diameter from DN130 to DN100 to enhance self-cleaning capacity.In addition,thermal insulation should be applied during winter operation to maintain the pipe wall temperature above 10◦C,thereby suppressing condensation-induced liquid accumulation.展开更多
Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and ca...Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.展开更多
The methane adsorption capacity,gas content,and carbon isotope characteristics of coal are crucial parameters that determine the productivity of coalbed methane(CBM)wells and their development potential.In this paper,...The methane adsorption capacity,gas content,and carbon isotope characteristics of coal are crucial parameters that determine the productivity of coalbed methane(CBM)wells and their development potential.In this paper,test analyses of methane adsorption,gas content and carbon isotope of methane were carried out using 89 samples from the No.3 coal seam in the southwestern part of the Qinshui Basin.Their characteristics and correlations were analyzed.A relationship model between methane adsorption,gas content,carbon isotopes,coal metamorphism and material composition were established,and its controlling mechanism was investigated.The results indicate that the distribution patterns of Langmuir volume and Langmuir pressure in No.3 coal seam are mainly determined by the material composition and the thermal evolution level.The methane gas content in coal is mainly affected by the burial depth,microcosmic co mposition,mineral conte nt,moisture content and ash yield,adsorption capacity and metamorphism of the coal.The methane carbon isotope(δ^(13)C_(1))values in the natural desorbed gas from No.3 coal seam range from-26.95%to-57.80‰,with a mean value of-34.53‰.δ^(13)C_(1)in coal shows a two-stage variation pattern with increasing in vitrinite reflectance(R_(max)^(o)).When R_(max)^(o)is blow 3.0%,δ^(13)C_(1)values of methane in coal become progressively heavier with increasing R_(max)^(o).When R_(max)^(o)reaches or exceeds 3.0%,δ^(13)C_(1)values exhibit a lightning trend with furth er increases in R_(max)^(o),which is primarily controlled by the carbon isotope fractionation effects during thermal evolution.展开更多
The sustainability of methane catalytic decomposition is significantly enhanced by the production of high-quality value-added carbon products such as carbon nanotubes(CNTs).Understanding the production yields and prop...The sustainability of methane catalytic decomposition is significantly enhanced by the production of high-quality value-added carbon products such as carbon nanotubes(CNTs).Understanding the production yields and properties of CNTs is crucial for improving process feasibility and sustainability.This study employs machine learning technique to develop and analyze predictive models for the carbon yield and mean diameter of CNTs produced through methane catalytic decomposition.Utilizing comprehensive datasets from various experimental studies,the models incorporate variables related to catalyst composition,catalyst preparation,and operational parameters.Both models achieved high predictive accuracy,with R^(2)values exceeding 0.90.Notably,the reduction time during catalyst preparation was found to critically influence carbon yield,evidenced by a permutation importance value of 39.62%.Additionally,the use of Mo as a catalytic metal was observed to significantly reduce the diameter of produced CNTs.These findings highlight the need for future machine learning and simulation studies to include catalyst reduction parameters,thereby enhancing predictive accuracy and deepening process insights.This research provides strategic guidance for optimizing methane catalytic decomposition to produce enhanced CNTs,aligning with sustainability goals.展开更多
The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-a...The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-atom anchored on the defective carbon nitride structure(Cu SA/Def-CN)is designed for selective photocatalytic oxidation of methane into methanol using O_(2) under mild conditions.The Cu SA/Def-CN catalyst exhibits a high methanol selectivity of 92.8%under optimized conditions.Mechanistic studies reveal a synergistic effect between Def-CN and Cu SA,where Def-CN is responsible for the in-situ generation of hydrogen peroxide,which is subsequently decomposed by the Cu SA sites to produce·OH radicals that play a key role in the rate-determining step of methane activation to form methanol.Additionally,the presence of Cu SA not only enhances the electron-hole separation efficiency and improves the transfer of the photo-generated charges,but also increases the number of active sites for methane adsorption and activation.These insights provide valuable guidance for designing efficient catalysts for the highly selective photocatalytic oxidation of methane to methanol.展开更多
Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving ...Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.展开更多
Based on the coalbed methane(CBM)/coal-rock gas(CRG)geological,geophysical,and experimental testing data from the Daji block in the Ordos Basin,the coal-forming and hydrocarbon generation&accumulation characterist...Based on the coalbed methane(CBM)/coal-rock gas(CRG)geological,geophysical,and experimental testing data from the Daji block in the Ordos Basin,the coal-forming and hydrocarbon generation&accumulation characteristics across different zones were dissected,and the key factors controlling the differential CBM/CRG enrichment were identified.The No.8 coal seam of the Carboniferous Benxi Formation in the Daji block is 8-10 m thick,typically overlain by limestone.The primary hydrocarbon generation phase occurred during the Early Cretaceous.Based on the differences in tectonic evolution and CRG occurrence,and with the maximum vitrinite reflectance of 2.0%and burial depth of 1800 m as boundaries,the study area is divided into deeply buried and deeply preserved,deeply buried and shallowly preserved,and shallowly buried and shallowly preserved zones.The deeply buried and deeply preserved zone contains gas content of 22-35 m^(3)/t,adsorbed gas saturation of 95%-100%,and formation water with total dissolved solid(TDS)higher than 50000 mg/L.This zone features structural stability and strong sealing capacity,with high gas production rates.The deeply buried and shallowly preserved zone contains gas content of 16-20 m^(3)/t,adsorbed gas saturation of 80%-95%,and formation water with TDS of 5000-50000 mg/L.This zone exhibits localized structural modification and hydrodynamic sealing,with moderate gas production rate.The shallowly buried and shallowly preserved zone contains gas content of 8-16 m^(3)/t,adsorbed gas saturation of 50%-70%,and formation water with TDS lower than 5000 mg/L.This zone experienced intense uplift,resulting in poor sealing and secondary alteration of the primary gas reservoir,with partial adsorbed gas loss,and low gas production rate.A depositional unification and structural divergence model is proposed,that is,although coal seams across the basin experienced broadly similar depositional and tectonic histories,differences in tectonic intensity have led to spatial heterogeneity in the maximum burial depth(i.e.,thermal maturity of coal)and current burial depth and occurrence of CRG(i.e.,gas content and occurrence state).The research results provide valuable guidance for advancing the theoretical understanding of CBM/CRG enrichment and for improving exploration and development practices.展开更多
Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a...Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a rational utilization of these biodegradable organic wastes,which is of vital importance for alleviating environmental deterioration and reducing resource waste.Electrode materials and accelerants are the two major factors that affect methane production in the MEC-AD system.They affect microbial attachment and electron transfer in the MEC-AD system.Bio-based carbon materials are carbon materials prepared from biomass as raw materials.They have characteristics such as a rich pore structure,good chemical stability,biocompatibility,and controllable surface properties,which can be used as accelerants and electrodes in the MEC-AD system to optimize its performance.This study was to investigate the influence of biomass-derived carbon as an electrode and accelerant on the performance of the MEC-AD system,and the mechanism for increasing the production of biogas and methane was also analyzed,thus providing a basis for the multifunctional application of biomass-derived carbon in the MEC-AD system.Methods A series of experimental methods were adopted to study the MEC-AD system.Two types of bio-based carbon,i.e.,aloe vera waste derived spherical carbon(AVW-SC)and porous carbon(AVW-PC),were synthesized via hydrothermal carbonization.The raw AVW material was washed with water,dried,ground,and subjected to hydrothermal treatment to obtain AVW-SC.After activating AVW-SC with KOH,it was carbonized in a tube furnace to obtain AVW-PC.In the preparation of the electrodes,bio-based carbon(AVW-SC and AVW-PC)was mixed with 5%polytetrafluoroethylene powder in ethanol and deionized water,and then ground in a ball mill for 4 h to form a slurry.The slurry was evenly sprayed on the Ti mesh,dried and sintered in N2 atmosphere at 360℃to obtain Ti-SC and Ti-PC electrodes.Four groups of experiments were conducted to determine the optimal voltage,compare different carbon electrodes,and explore the optimal coating amount.The MEC-AD reactor adopted 500 mL wide-mouthed glass bottles with a working volume of 400 mL.Each MEC-AD system received a co-substrate mixture of cattle dung and aloe vera waste and inoculum of sewage sludge in a mass ratio of 3:7.Afterward,they were placed at(36±1)℃for 35 d.The biogas was collected by a water displacement method.The materials were analyzed by characterization techniques such as X-ray diffraction(XRD)and scanning electron microscopy(SEM),and electrochemical tests were conducted on different electrodes.The composition,pH,TS,VS,TCOD and nutrient content of biogas were analyzed by standard chemical methods.Microbial community analysis was conducted using high-throughput sequencing technology.The modified Gompertz model was adopted to predict the kinetic parameters,and the coulombic efficiency and methane recovery rate were calculated according to a specific formula.Results and discussion The result shows that AVW-SC is spherical and closely aggregated,while AVW-PC has a three-dimensional network structure,with average pore diameter of 9.77 nm.The electron exchange capacity(EEC)of AVW-PC(i.e.,0.75μmol·e-/g)is higher than that of AVW-SC(i.e.,0.15μmol·e-/g),indicating a better electron exchange capacity.These results indicate that AVW-PC provides more substrate and bacteria accumulation sites,and has better electron-donating and electron-accepting ability,thus improving the digestion efficiency.In the MEC-AD system,using Ti mesh as an electrode,the effect of different voltages(i.e.,0,0.4,0.6,0.8 V and 1.2 V)on the system performance is investigated,obtaining the optimum biogas production and organic matter degradation rate at 0.8 V.AVW-SC and AVW-PC are respectively coated on Ti mesh as electrodes.The results show that the MEC-AD system with AVW-PC coated Ti mesh as the electrode has a better performance.The electrochemical analysis shows that the electrode coated with AVW-PC has a larger specific capacitance and a smaller charge transfer resistance,indicating that AVW-PC can improve the electrochemical properties and electron transfer ability of MEC-AD system.The influence of coating amount(i.e.,0.025,0.05,0.10,0.15,and 0.20 g)of AVW-PC on the MEC-AD system is investigated.At a coating amount of AVW-PC of 0.1 g,the cumulative biogas production and methane content of the Ti_(0.8)-PC_90.1) group both reach the maximum values.Different doses of AVW-PC(i.e.,0.10%,0.15%,0.20%,and 0.25%)are added as accelerants in Ti_(0.8)-PC_90.1).At the addition amount of AVW-PC of 0.20%,the Ti_(0.8)-PC_90.1)/PC0.2 group performs the optimum biogas production(i.e.,633.63 mL/g VS),methane content(i.e.,65.85%),and total nutrient content of biogas residue(i.e.,42.30 g/kg).In Ti_(0.8)-PC_90.1)/PC0.2,Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinacea and Methanosaetaceae significantly increase.The increase in microbial diversity promotes interspecific hydrogen transfer(IHT),interspecific acetic transfer(IAT),and direct interspecific electron transfer(DIET),thereby enhancing methanogenic efficiency.Conclusions AVW-SC and AVW-PC were utilized as electrodes and accelerants to enhance methane yield in MEC-AD system.The Ti mesh electrode coated with different concentrations of AVW-PC achieved the optimal biogas production at 0.8 V.Specifically,the Ti_(0.8)-PC_90.1) combination could generate the maximum total amount of biogas and methane proportion.The Ti_(0.8)-PC_90.1)/PC0.2 combination exhibited the optimum performance(i.e.,biogas yield of 633.63 mL/g VS,methane content of 65.85%and total nutritional content of 42.30 g/kg).High abundances of Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinaceae,and Methanosaetaceae appeared in the Ti_(0.8)-PC_90.1)/PC0.2 group,compared to other groups.In addition,an increased microbial diversity led to an enhanced methane production through processes like DIET.This research could highlight the potential significance of AVW-PC as both electrode and accelerator for increasing methane production and provide a perspective for improving MEC-AD performance through multiple applications of biomass-derived carbon.展开更多
SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhance...SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.展开更多
In order to investigate the CH4 and CO2 fluxes across the water-gas interface and identify their controlling factors, four diel field campaigns and one monthly sampling campaign during June 2010-May 2011 were carried ...In order to investigate the CH4 and CO2 fluxes across the water-gas interface and identify their controlling factors, four diel field campaigns and one monthly sampling campaign during June 2010-May 2011 were carried out at a site near the Three Gorges Dam, China. The averaged CH4 and CO2 fluxes across the air-water interface from the site were much less than those reported from reservoirs in tropic and temperate regions, and from the natural river channels of the Yangtze River. CH4 Fluxes at the site were very low compared to most other reservoirs or natural lakes. One of the most important reasons may be due to the oxidation of CH4 in the water column owing to the great water depth and high DO in water in the Three Gorges Reservoir. The averaged monthly CH4 and CO2 fluxes at the site during the observation year were 0.05 mg/（m^2·hr） and 104.43 mg/（m^2·hr） respectively with the maximum occurred in July 2010. The monthly CO2 fluxes during the observation year were positively correlated to the surface water temperature, and negatively correlated to the air pressure and the surface water pH. The CO2 flux showed a positive correlation with DOC to some extent, although not significantly, which indicated that allochthonous organic C was a major source of CO2 and biogeochemical processes in this reservoir were C-limited. The significantly positive correlation between the reservoir outflow and the seasonal gas flux indicate the disturbance condition of the water body dominated the seasonal gas emission.展开更多
A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were cha...A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.展开更多
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
基金Supported by Innovative Research Groups of the National Natural Science Foundation of China(22021004)。
文摘Catalytic decomposition of methane,which produces high-purity hydrogen and high-value-added carbon nanomaterials,has shown considerable potential for development and is expected to yield significant economic benefits in the future.However,designing catalysts that simultaneously exhibit high activity and long-term stability remains a significant challenge.Tuning the catalyst’s structure and electronic properties is an effective strategy for enhancing the reaction performance.In this work,a series of NixZr/ZSM-5 catalysts were prepared using the incipient wetness impregnation method,and the effect of Zr loadings on catalyst properties and performance was systematically investigated.The calcined and reduced catalysts were characterized by low-temperature N_(2)adsorption-desorption,XRD,SEM,H_(2)-TPR and XPS.The results showed that the addition of Zr significantly increased the specific surface area of the catalyst and reduced the metal particle size.Smaller NiO particles were found to enter the pores of the HZSM-5 support,and electronic interactions between NiO and ZrO_(2)markedly enhanced the metal-support interaction.The catalyst exhibited optimal catalytic performance at a Zr loading of 5%,achieving a maximum methane conversion of 68%at 625℃,maintaining activity for 900 min,and delivering a carbon yield of 1927%.Further increasing the Zr loading yielded only limited improvements in catalytic performance.Characterization of the spent catalysts and carbon products via TEM,Raman spectroscopy,and TGA revealed that the introduction of ZrO_(2)reduced metal sintering and promoted a shift in carbon nanofibers growth mode from tip-growth to base-growth.The mechanism of base-growth enabled the catalyst to maintain reaction activity for an extended period.
文摘The objective of this study is to propose an optimal plant design for blue hydrogen production aboard a liquefiednatural gas(LNG)carrier.This investigation focuses on integrating two distinct processes—steam methanereforming(SMR)and ship-based carbon capture(SBCC).The first refers to the common practice used to obtainhydrogen from methane(often derived from natural gas),where steam reacts with methane to produce hydrogenand carbon dioxide(CO_(2)).The second refers to capturing the CO_(2) generated during the SMR process on boardships.By capturing and storing the carbon emissions,the process significantly reduces its environmental impact,making the hydrogen production“blue,”as opposed to“grey”(which involves CO_(2) emissions without capture).For the SMR process,the analysis reveals that increasing the reformer temperature enhances both the processperformance and CO_(2) emissions.Conversely,a higher steam-to-carbon(s/c)ratio reduces hydrogen yield,therebydecreasing thermal efficiency.The study also shows that preheating the air and boil-off gas(BOG)before theyenter the combustion chamber boosts overall efficiency and curtails CO_(2) emissions.In the SBCC process,puremonoethanolamine(MEA)is employed to capture the CO_(2) generated by the exhaust gases from the SMR process.The results indicate that with a 90%CO_(2) capture rate,the associated heat consumption amounts to 4.6 MJ perkilogram of CO_(2) captured.This combined approach offers a viable pathway to produce blue hydrogen on LNGcarriers while significantly reducing the carbon footprint.
基金funded by the Beef Cattle Research Council Cluster(FDE.18.21C)Natural Sciences and Engineering Research Council of Canada(NSERC)Discovery,NSERC Canadian Research Chair(Tier 1)program+2 种基金NSERC Alliance program(ALLRP 588541‐23)Foundation for Food&Agriculture Research Greener Cattle Initiative(Award ID 22‐000373)DSM Nutritional Products,Kaiseraugst,Switzerland。
文摘Background The enteric methane inhibitor 3-nitrooxypropanol(3-NOP)inhibits the key enzyme in ruminal methanogenesis,but whether short-term(ST)and long-term(LT)dietary supplementation has similar effects on rumen microbiota in beef cattle and how microbes change after 3-NOP withdrawal have not been studied.This study investigated changes in rumen bacteria,archaea,and protozoa after ST and LT dietary supplementation and removal of 3-NOP using metataxonomic analysis.Results A total of 143 rumen samples were collected from two beef cattle studies with 3-NOP supplementation.The ST study(95 samples)used eight ruminally cannulated beef cattle in a 4×4 Latin square design with four 28-d of 3-NOP treatments[mg/kg of dry matter(DM)]:control:0,low:53,med:161,and high:345.The LT study(48 samples)was a completely randomized design with two 3-NOP treatments[control:0,and high:280 mg/kg of DM)fed for 112-d followed by a 16-d withdrawal(without 3-NOP).Bacterial and archaeal communities were significantly affected by 3-NOP supplementation but limited effects on protozoal communities were observed.Under ST supplementation,the relative abundances of Prevotella,Methanobrevibacter(Mbb.)ruminantium,Methanosphaera sp.ISO3-F5,and Entodinium were increased(Q<0.05),whereas those of Mbb.gottschalkii and Epidinium were decreased(Q<0.05)with 3-NOP supplementation.In LT study,relative abundances of Mbb.ruminantium,and Methanosphaera sp.Group5 were increased(Q<0.05),while those of Saccharofermentans and Mbb.gottschalkii were decreased(Q<0.05)with 3-NOP supplementation.Comparison between 3-NOP supplementation and the withdrawal revealed increased relative abundances of Clostridia UCG-014 and Oscillospiraceae NK4A214 group and decreased those of Eubacterium nodatum group and Methanosphaera sp.Group5(P<0.05)after 3-NOP withdrawal.Further comparison of rumen microbiota between control and 3-NOP withdrawal showed significantly higher(P=0.029)relative abundances of Eggerthellaceae DNF00809,p-1088-a5 gut group,and Family XII UCG-001 in control group while no significant differences were detected for archaea and protozoa.Microbial network analysis revealed that microbial interactions differed by both 3-NOP dose and durations.Conclusions Both ST and LT supplementation affected overall rumen microbial profile,with individual microbial groups responded to 3-NOP supplementation differently.After 3-NOP withdrawal,not all microbes showed recovery,indicating that the 3-NOP driven shifts were only partially reversible.These findings provide an understanding of the effects of 3-NOP on rumen microbial communities and their adaptability to methane mitigation strategies.
基金the financial support from National Natural Science Foundation of China(No.52474029)Strategic and Applied Scientific Research Project of PetroChina Company Limited(2023ZZ18,2023ZZ18YJ04).
文摘In the development of coalbed methane(CBM)reservoirs using multistage fractured horizontal wells,there often exist areas that are either repeatedly stimulated or completely unstimulated between fracturing stages,leading to suboptimal reservoir performance.Currently,there is no well-established method for accurately evaluating the effectiveness of such stimulation.This study introduces,for the first time,the concept of the Fracture Network Bridging Coefficient(FNBC)as a novel metric to assess stimulation performance.By quantitatively coupling the proportions of unstimulated and overstimulated volumes,the FNBC effectively characterizes the connectivity and efficiency of the fracture network.A background grid calibration method is developed to quantify the stage-controlled volume,effectively stimulated volume,unstimulated volume,and repeatedly stimulated volume among different stages of horizontal wells.Furthermore,an optimization model is constructed by taking the FNBC as the objective function and the fracturing injection rate and fluid volume as optimization variables.The Simultaneous Perturbation Stochastic Approximation(SPSA)algorithm is employed to iteratively perturb and optimize these variables,progressively improving the FNBC until the optimal displacement rate and fluid volume corresponding to the maximum FNBC are obtained.Field application in a typical CBM multistage fractured horizontal well in China demonstrates that the FNBC increased from 0.358 to 0.539(a 50.6% improvement),with the injection rate rising from 16 m^(3)/min to 24 m^(3)/min and the average fluid volume per stage increasing from 2490 m^(3) to 3192 m^(3),significantly enhancing the stimulation effectiveness.This research provides theoretical support for designing high-efficiency stimulation strategies in unconventional reservoirs under dynamic limits.
文摘Recent research progress on the use of Ni-based catalysts supported by various carbon materials,such as carbon nanotubes,graphene,and activated carbon,for the hydrogenation of CO_(2)to CH_(4) is summarized.The influence of additives and surface modification methods on improving their catalytic performance is discussed as is the reaction mechanism,especially the structurefunction relationship produced by the carbon.The review provides a comprehensive directory for the rational design of carbon-supported Ni-based catalysts for the methanation of CO_(2).
基金supported by the National Science and Technology Major Project of China(No.2025ZD1405702)the Scientific Research and Technology Development Project of PetroChina Coalbed Methane Co.,Ltd.(Project No.25MQCTSG010)Applied Science and Technology Project of PetroChina Company Limited(2023ZZ18YJ04).
文摘Significant differences exist between deep and medium-shallow coalbed methane(CBM)reservoirs.The unclear understanding of flowback and production behavior severely constrains the development of deep CBM resources.To address this challenge,guided by the gas-liquid two-phase flow theory in ultra-low permeability reservoirs,and integrating theoretical analysis,numerical simulation,and insights from production practices,this study classifies the flowback and production stages of deep CBM well considering the Daning-Jixian Block,Eastern Ordos Basin as a representative case.We summarize the flowback characteristics for each stage and establish a standard flowback production type curve,aiming to guide field operations.The results indicate that:(a)The production process of deep CBM horizontal wells can be divided into five distinct stages:initial single-phase water dewatering stage,initial gas appearance to peak water production stage,gas breakthrough to peak gas production stage,stable production and decline stage,and low-rate production stage.(b)Based on reservoir energy,two standard type curves for horizontal well flowback production are established:the‘Sufficient Reservoir Energy’type and the‘Insufficient Reservoir Energy’type.The former achieves a higher initial gas rate(up to 12×10^(4)m^(3)/d)but exhibits poorer stability,while the latter achieves a lower stable rate(up to 8×10^(4)m^(3)/d)but demonstrates stronger stability.Numerical simulation confirms these behavioral patterns and reveals the underlying mechanisms related to the effectively drained area where pressure is significantly depleted.The findings from this study have guided the flowback production operations in 53 deep CBM wells with positive results,demonstrating high potential for broad application.
基金funded by the Integrated Demonstration of Scalable and Efficient Healthy Breeding for Cattle and Sheep(Grant No.2022YFD1301100)Instant Intelligent Diagnosis and Risk Warning Methods for Nutritional and Metabolic-Type Periparturient Cow Paralysis(Grant No.2024-YWF-ZYSQ-10)。
文摘Background Methane(CH_(4))emissions from ruminants significantly contribute to greenhouse gas effects and energy loss in livestock production.Methyl-coenzyme M reductase(MCR)is the key enzyme in methanogenesis,making it a promising target for CH_(4) mitigation.This study aimed to identify and validate plant-derived inhibitors by using molecular docking to screen compounds with strong binding affinity to the F430 active site of MCR and assessing their efficacy in reducing CH_(4) emissions.Results Molecular docking analysis identified salvianolic acid C(SAC)as a potent inhibitor of MCR,showing a strong binding affinity to the F430 active site(binding energy:-8.2 kcal/mol).Enzymatic inhibition assays confirmed its inhibitory effect,with a half-maximal inhibitory concentration(IC50)of 692.3μmol/L.In vitro rumen fermentation experiments demonstrated that SAC supplementation(1.5 mg/g DM)significantly reduced CH_(4)production(P<0.01)without negatively affecting major fermentation parameters.Microbial community analysis using 16S rRNA sequencing and metagenomics revealed that SAC selectively altered the rumen microbiota,increasing the relative abundance of Bacteroidota while significantly reducing Methanobrevibacter(P=0.04).Moreover,metagenomic analysis showed the downregulation of key methanogenesis-related genes(mcrA and rnfC),suggesting a dual mechanism involving direct enzymatic inhibition and microbial community modulation.Conclusions These findings indicate that SAC effectively reduces CH_(4)production by inhibiting MCR activity and reshaping the rumen microbial community.As a plant-derived compound with strong inhibitory effects on methanogenesis,SAC presents a promising and sustainable alternative to synthetic CH_(4) inhibitors,offering potential applications for mitigating CH_(4)emissions in livestock production.
基金support from the Zhejiang Provincial Natural Science Foundation of China (No.LQ24B030011)the Ningbo Natural Science Foundation (No.2023J181)+4 种基金the Open Research Fund of Key Laboratory of Functional Inorganic Materials Chemistry of the Ministry of Education (Heilongjiang University)the Start-up Funding offered by Ningbo University of Technology to J.D.LiNational Natural Science Foundation of China (No.U24A2071)Postdoctoral Research Start-up Fund (No.2111224002)Harbin Normal University Talent Plan (No.1305124213) to Y.D.Liu。
文摘The photocatalytic oxidation of methane(CH_(4)) to valuable chemicals like low alcohols(CH_(3)OH and C_(2)H_(5)OH) represents a significant technological advancement with implications for energy conversion and environmental purification.A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes,which can lead to over-oxidation and reduced selectivity and efficiency.To address these issues,we have developed a sodium-doped zinc oxide(Na-ZnO) modified with cobalt oxide(CoO) catalyst.This catalyst has demonstrated excellent performance in converting methane to low alcohols,achieving a yield of 130 μmol g^(-1)h^(-1) and a selectivity of up to 96 %.The doping of Na in ZnO significantly enhances methane adsorption,while the surface-modified CoO effectively captures photogenerated holes,activates water molecules,and uses hydroxyl radicals to activate methane,thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products.This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols,offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
基金supported by PetroChina Coalbed Methane Co.,Ltd.
文摘With the maturation of coalbed methane(CBM)exploitation and the transition into the late stages of dewatering and gas production,liquid loading in gathering pipelines has emerged as a major constraint on productivity and operational stability.Based on real-time field data and gas-liquid physicochemical analyses,this study elucidates the mechanisms governing liquid loading formation under varying temperature,pressure,and water saturation conditions.An HYSYS model is employed to determine the water dew point,while the Turner model is used to evaluate the critical conditions for liquid holdup.The results indicate that gas water saturation exerts the dominant influence on liquid loading risk,followed by pressure,whereas temperature plays a comparatively minor role.When water saturation exceeds 2%and the operating temperature falls below the dew point,condensation-driven liquid loading increases sharply.To further characterize the spatial distribution of liquid accumulation,a steady-state OLGA model of a DN100 gathering pipeline network is developed to examine the effects of pipe diameter,water saturation,and soil temperature.The simulations show that larger pipe diameters and higher water saturation significantly aggravate liquid holdup,while elevated soil temperature mitigates liquid accumulation.Moreover,the liquid holdup ratio is found to correlate closely with flow regime transitions,confirming its suitability as a key indicator of liquid loading risk.Based on these findings,optimization strategies for pipeline design and operation are proposed.To mitigate liquid loading,the gathering pipeline velocity should be maintained above the critical value of 1.63 m/s,and the gas water content should be strictly controlled below 2%.Under operating conditions representative of the Hancheng block,it is recommended to reduce the pipeline diameter from DN130 to DN100 to enhance self-cleaning capacity.In addition,thermal insulation should be applied during winter operation to maintain the pipe wall temperature above 10◦C,thereby suppressing condensation-induced liquid accumulation.
基金National Key R&D Program of China (2023YFA1508001 and 2023YFA1508002)National Natural Science Foundation of China (22272120 and U2202251)+1 种基金Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ120)Research Foundation of Marine Science and Technology Collaborative Innovation Center of Hainan University (XTCX2022HYB01)。
文摘Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.
基金supported by the National Natural Science Foundation of China(No.42372192)Shanxi Province science and technology plan joint unveiling project(No.20201101002)。
文摘The methane adsorption capacity,gas content,and carbon isotope characteristics of coal are crucial parameters that determine the productivity of coalbed methane(CBM)wells and their development potential.In this paper,test analyses of methane adsorption,gas content and carbon isotope of methane were carried out using 89 samples from the No.3 coal seam in the southwestern part of the Qinshui Basin.Their characteristics and correlations were analyzed.A relationship model between methane adsorption,gas content,carbon isotopes,coal metamorphism and material composition were established,and its controlling mechanism was investigated.The results indicate that the distribution patterns of Langmuir volume and Langmuir pressure in No.3 coal seam are mainly determined by the material composition and the thermal evolution level.The methane gas content in coal is mainly affected by the burial depth,microcosmic co mposition,mineral conte nt,moisture content and ash yield,adsorption capacity and metamorphism of the coal.The methane carbon isotope(δ^(13)C_(1))values in the natural desorbed gas from No.3 coal seam range from-26.95%to-57.80‰,with a mean value of-34.53‰.δ^(13)C_(1)in coal shows a two-stage variation pattern with increasing in vitrinite reflectance(R_(max)^(o)).When R_(max)^(o)is blow 3.0%,δ^(13)C_(1)values of methane in coal become progressively heavier with increasing R_(max)^(o).When R_(max)^(o)reaches or exceeds 3.0%,δ^(13)C_(1)values exhibit a lightning trend with furth er increases in R_(max)^(o),which is primarily controlled by the carbon isotope fractionation effects during thermal evolution.
基金supported by the Agency for Science,Technology and Research(A*STAR),Singapore,under the project Methane Pyrolysis for Hydrogen and Carbon Nanotube Production via Novel Catalytic Membrane Reactor System(No.U2102d2011)。
文摘The sustainability of methane catalytic decomposition is significantly enhanced by the production of high-quality value-added carbon products such as carbon nanotubes(CNTs).Understanding the production yields and properties of CNTs is crucial for improving process feasibility and sustainability.This study employs machine learning technique to develop and analyze predictive models for the carbon yield and mean diameter of CNTs produced through methane catalytic decomposition.Utilizing comprehensive datasets from various experimental studies,the models incorporate variables related to catalyst composition,catalyst preparation,and operational parameters.Both models achieved high predictive accuracy,with R^(2)values exceeding 0.90.Notably,the reduction time during catalyst preparation was found to critically influence carbon yield,evidenced by a permutation importance value of 39.62%.Additionally,the use of Mo as a catalytic metal was observed to significantly reduce the diameter of produced CNTs.These findings highlight the need for future machine learning and simulation studies to include catalyst reduction parameters,thereby enhancing predictive accuracy and deepening process insights.This research provides strategic guidance for optimizing methane catalytic decomposition to produce enhanced CNTs,aligning with sustainability goals.
文摘The photocatalytic oxidation of methane to methanol using molecule oxygen directly is an attractive catalytic reaction,but designing catalysts to avoid over-oxidation remains a significant challenge.Herein,Cu single-atom anchored on the defective carbon nitride structure(Cu SA/Def-CN)is designed for selective photocatalytic oxidation of methane into methanol using O_(2) under mild conditions.The Cu SA/Def-CN catalyst exhibits a high methanol selectivity of 92.8%under optimized conditions.Mechanistic studies reveal a synergistic effect between Def-CN and Cu SA,where Def-CN is responsible for the in-situ generation of hydrogen peroxide,which is subsequently decomposed by the Cu SA sites to produce·OH radicals that play a key role in the rate-determining step of methane activation to form methanol.Additionally,the presence of Cu SA not only enhances the electron-hole separation efficiency and improves the transfer of the photo-generated charges,but also increases the number of active sites for methane adsorption and activation.These insights provide valuable guidance for designing efficient catalysts for the highly selective photocatalytic oxidation of methane to methanol.
文摘Photothermal catalytic methane dry reforming(DRM)technology can convert greenhouse gases(i.e.CH_(4)and CO_(2))into syngas(i.e.H_(2)and CO),providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality.In the DRM field,Ni-based catalysts attract wide attention due to their low cost and high activity.However,the carbon deposition over Ni-based catalysts always leads to rapid deactivation,which is still a main challenge.To improve the long-term stability of Ni-based catalysts,this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst(Ni_(3)Zn@CeO_(2)).The photothermal catalytic behavior of Ni_(3)Zn@CeO_(2)can maintain more than 70 h in DRM reaction.And the photocatalytic DRM activity of Ni_(3)Zn@CeO_(2)is 1.2 times higher than thermal catalytic activity.Density functional theory(DFT)calculation and experimental characterizations indicate that Ni_(3)Zn promotes the diffusion of carbon atoms into the Ni_(3)Zn to form the Ni_(3)ZnC0.7 phase with body-centered cubic(bcc)structure,thus inhibiting carbon deposition.Further,in-situ diffuse reflectance infrared Fourier transform(DRIFT)spectroscopy and DFT calculation prove Ni_(3)Zn@CeO_(2)benefits the CH_(4)activation and inhibits the carbon deposition during the DRM process.Through inducing carbon atoms diffusion within the Ni_(3)Zn lattice,this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH_(4)conversion implementations with long-term stability.
基金Supported by the China National Science and Technology Major Project(2025ZD1405700)CNPC Science and Technology Project(2023YQX20117).
文摘Based on the coalbed methane(CBM)/coal-rock gas(CRG)geological,geophysical,and experimental testing data from the Daji block in the Ordos Basin,the coal-forming and hydrocarbon generation&accumulation characteristics across different zones were dissected,and the key factors controlling the differential CBM/CRG enrichment were identified.The No.8 coal seam of the Carboniferous Benxi Formation in the Daji block is 8-10 m thick,typically overlain by limestone.The primary hydrocarbon generation phase occurred during the Early Cretaceous.Based on the differences in tectonic evolution and CRG occurrence,and with the maximum vitrinite reflectance of 2.0%and burial depth of 1800 m as boundaries,the study area is divided into deeply buried and deeply preserved,deeply buried and shallowly preserved,and shallowly buried and shallowly preserved zones.The deeply buried and deeply preserved zone contains gas content of 22-35 m^(3)/t,adsorbed gas saturation of 95%-100%,and formation water with total dissolved solid(TDS)higher than 50000 mg/L.This zone features structural stability and strong sealing capacity,with high gas production rates.The deeply buried and shallowly preserved zone contains gas content of 16-20 m^(3)/t,adsorbed gas saturation of 80%-95%,and formation water with TDS of 5000-50000 mg/L.This zone exhibits localized structural modification and hydrodynamic sealing,with moderate gas production rate.The shallowly buried and shallowly preserved zone contains gas content of 8-16 m^(3)/t,adsorbed gas saturation of 50%-70%,and formation water with TDS lower than 5000 mg/L.This zone experienced intense uplift,resulting in poor sealing and secondary alteration of the primary gas reservoir,with partial adsorbed gas loss,and low gas production rate.A depositional unification and structural divergence model is proposed,that is,although coal seams across the basin experienced broadly similar depositional and tectonic histories,differences in tectonic intensity have led to spatial heterogeneity in the maximum burial depth(i.e.,thermal maturity of coal)and current burial depth and occurrence of CRG(i.e.,gas content and occurrence state).The research results provide valuable guidance for advancing the theoretical understanding of CBM/CRG enrichment and for improving exploration and development practices.
文摘Introduction The generation of biological wastes such as cow dung and aloe vera waste(AVW)causes a serious ecological pollution.The microbial electrolytic cell coupled with anaerobic digestion(MEC-AD)system can make a rational utilization of these biodegradable organic wastes,which is of vital importance for alleviating environmental deterioration and reducing resource waste.Electrode materials and accelerants are the two major factors that affect methane production in the MEC-AD system.They affect microbial attachment and electron transfer in the MEC-AD system.Bio-based carbon materials are carbon materials prepared from biomass as raw materials.They have characteristics such as a rich pore structure,good chemical stability,biocompatibility,and controllable surface properties,which can be used as accelerants and electrodes in the MEC-AD system to optimize its performance.This study was to investigate the influence of biomass-derived carbon as an electrode and accelerant on the performance of the MEC-AD system,and the mechanism for increasing the production of biogas and methane was also analyzed,thus providing a basis for the multifunctional application of biomass-derived carbon in the MEC-AD system.Methods A series of experimental methods were adopted to study the MEC-AD system.Two types of bio-based carbon,i.e.,aloe vera waste derived spherical carbon(AVW-SC)and porous carbon(AVW-PC),were synthesized via hydrothermal carbonization.The raw AVW material was washed with water,dried,ground,and subjected to hydrothermal treatment to obtain AVW-SC.After activating AVW-SC with KOH,it was carbonized in a tube furnace to obtain AVW-PC.In the preparation of the electrodes,bio-based carbon(AVW-SC and AVW-PC)was mixed with 5%polytetrafluoroethylene powder in ethanol and deionized water,and then ground in a ball mill for 4 h to form a slurry.The slurry was evenly sprayed on the Ti mesh,dried and sintered in N2 atmosphere at 360℃to obtain Ti-SC and Ti-PC electrodes.Four groups of experiments were conducted to determine the optimal voltage,compare different carbon electrodes,and explore the optimal coating amount.The MEC-AD reactor adopted 500 mL wide-mouthed glass bottles with a working volume of 400 mL.Each MEC-AD system received a co-substrate mixture of cattle dung and aloe vera waste and inoculum of sewage sludge in a mass ratio of 3:7.Afterward,they were placed at(36±1)℃for 35 d.The biogas was collected by a water displacement method.The materials were analyzed by characterization techniques such as X-ray diffraction(XRD)and scanning electron microscopy(SEM),and electrochemical tests were conducted on different electrodes.The composition,pH,TS,VS,TCOD and nutrient content of biogas were analyzed by standard chemical methods.Microbial community analysis was conducted using high-throughput sequencing technology.The modified Gompertz model was adopted to predict the kinetic parameters,and the coulombic efficiency and methane recovery rate were calculated according to a specific formula.Results and discussion The result shows that AVW-SC is spherical and closely aggregated,while AVW-PC has a three-dimensional network structure,with average pore diameter of 9.77 nm.The electron exchange capacity(EEC)of AVW-PC(i.e.,0.75μmol·e-/g)is higher than that of AVW-SC(i.e.,0.15μmol·e-/g),indicating a better electron exchange capacity.These results indicate that AVW-PC provides more substrate and bacteria accumulation sites,and has better electron-donating and electron-accepting ability,thus improving the digestion efficiency.In the MEC-AD system,using Ti mesh as an electrode,the effect of different voltages(i.e.,0,0.4,0.6,0.8 V and 1.2 V)on the system performance is investigated,obtaining the optimum biogas production and organic matter degradation rate at 0.8 V.AVW-SC and AVW-PC are respectively coated on Ti mesh as electrodes.The results show that the MEC-AD system with AVW-PC coated Ti mesh as the electrode has a better performance.The electrochemical analysis shows that the electrode coated with AVW-PC has a larger specific capacitance and a smaller charge transfer resistance,indicating that AVW-PC can improve the electrochemical properties and electron transfer ability of MEC-AD system.The influence of coating amount(i.e.,0.025,0.05,0.10,0.15,and 0.20 g)of AVW-PC on the MEC-AD system is investigated.At a coating amount of AVW-PC of 0.1 g,the cumulative biogas production and methane content of the Ti_(0.8)-PC_90.1) group both reach the maximum values.Different doses of AVW-PC(i.e.,0.10%,0.15%,0.20%,and 0.25%)are added as accelerants in Ti_(0.8)-PC_90.1).At the addition amount of AVW-PC of 0.20%,the Ti_(0.8)-PC_90.1)/PC0.2 group performs the optimum biogas production(i.e.,633.63 mL/g VS),methane content(i.e.,65.85%),and total nutrient content of biogas residue(i.e.,42.30 g/kg).In Ti_(0.8)-PC_90.1)/PC0.2,Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinacea and Methanosaetaceae significantly increase.The increase in microbial diversity promotes interspecific hydrogen transfer(IHT),interspecific acetic transfer(IAT),and direct interspecific electron transfer(DIET),thereby enhancing methanogenic efficiency.Conclusions AVW-SC and AVW-PC were utilized as electrodes and accelerants to enhance methane yield in MEC-AD system.The Ti mesh electrode coated with different concentrations of AVW-PC achieved the optimal biogas production at 0.8 V.Specifically,the Ti_(0.8)-PC_90.1) combination could generate the maximum total amount of biogas and methane proportion.The Ti_(0.8)-PC_90.1)/PC0.2 combination exhibited the optimum performance(i.e.,biogas yield of 633.63 mL/g VS,methane content of 65.85%and total nutritional content of 42.30 g/kg).High abundances of Bacteroidales,Pseudomonadales,Oscillospirales,Methanobacteraceae,Methanospirillaceae,Methanosarcinaceae,and Methanosaetaceae appeared in the Ti_(0.8)-PC_90.1)/PC0.2 group,compared to other groups.In addition,an increased microbial diversity led to an enhanced methane production through processes like DIET.This research could highlight the potential significance of AVW-PC as both electrode and accelerator for increasing methane production and provide a perspective for improving MEC-AD performance through multiple applications of biomass-derived carbon.
基金the financial support of this study from National Key Research and Development Program of China(No.2017YFB0603402)the National Natural Science Foundation of China(No.21576131,21938007 and 21366013)support of Jiangsu College Student Innovation Training Project(201910291049Z)。
文摘SSZ-13 membranes with high separation performances were prepared using ball-milled nanosized seeds by once hydrothermal synthesis.Separation performances of SSZ-13 membranes in CO2/CH4 and N2/CH4 mixtures were enhanced after synthesis modification.Single-gas permeances of CO2,N2 and CH4 and ideal selectivities were recorded through SSZ-13 membranes.The effects of temperature,pressure,feed flow rate and humidity on separation performance of the membranes were discussed.Three membranes prepared after synthesis modifications had an average CO2 permeance of 1.16×10-6 mol·(m2·s·Pa)-1(equal to 3554 GPU)with an average CO2/CH4 selectivity of 213 in a 50 vol%/50 vol%CO2/CH4 mixture.It suggests that membrane synthesis has a good reproducible.The membrane also displayed a N2 permeance of 1.07×10-7 mol·(m2·s·Pa)-1(equal to 320 GPU)with a N2/CH4 selectivity of 13 for a 50 vol%/50 vol%N2/CH4 mixture.SSZ-13 membrane displayed stable and good separation performance in the wet CO2/CH4 mixture for a long test period over 100 h at 348 K.The current SSZ-13 membranes show great potentials for the simultaneous removals of CO2 and N2 in natural gas purification as a facile process suitable for industrial application.
基金supported by National Science Foundation of China (No.41273110,51079163)the National Basic Research Program (973) of China(No.2010CB955904)State Key Laboratory of Loess and Quaternary Geology,Institute of Earth Environment,Chinese Academy of Sciences
文摘In order to investigate the CH4 and CO2 fluxes across the water-gas interface and identify their controlling factors, four diel field campaigns and one monthly sampling campaign during June 2010-May 2011 were carried out at a site near the Three Gorges Dam, China. The averaged CH4 and CO2 fluxes across the air-water interface from the site were much less than those reported from reservoirs in tropic and temperate regions, and from the natural river channels of the Yangtze River. CH4 Fluxes at the site were very low compared to most other reservoirs or natural lakes. One of the most important reasons may be due to the oxidation of CH4 in the water column owing to the great water depth and high DO in water in the Three Gorges Reservoir. The averaged monthly CH4 and CO2 fluxes at the site during the observation year were 0.05 mg/（m^2·hr） and 104.43 mg/（m^2·hr） respectively with the maximum occurred in July 2010. The monthly CO2 fluxes during the observation year were positively correlated to the surface water temperature, and negatively correlated to the air pressure and the surface water pH. The CO2 flux showed a positive correlation with DOC to some extent, although not significantly, which indicated that allochthonous organic C was a major source of CO2 and biogeochemical processes in this reservoir were C-limited. The significantly positive correlation between the reservoir outflow and the seasonal gas flux indicate the disturbance condition of the water body dominated the seasonal gas emission.
文摘A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.
