Screening the optimal Co_(x)/CeO_(2)(110)(x=1–6)catalyst for methane activation in coalbed gas

The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources.It is imperative to convert the abundant coalbed gas(CBG)into high value-added products,i.e.,selective and efficient conversion of methane from CBG.Methane activation,known as the“holy grail”,poses a challenge to the design and development of catalysts.The structural complexity of the active metal on the carrier is of particular concern.In this work,we have studied the nucleation growth of small Co clusters(up to Co_(6))on the surface of CeO_(2)(110)using density functional theory,from which a stable loaded Co/CeO_(2)(110)structure was selected to investigate the methane activation mechanism.Despite the relatively small size of the selected Co clusters,the obtained Co_(x)/CeO_(2)(110)exhibits interesting properties.The optimized Co_(5)/CeO_(2)(110)structure was selected as the optimal structure to study the activation mechanism of methane due to its competitive electronic structure,adsorption energy and binding energy.The energy barriers for the stepwise dissociation of methane to form CH3^(*),CH2^(*),CH^(*),and C^(*)radical fragments are 0.44,0.55,0.31,and 1.20 eV,respectively,indicating that CH^(*)dissociative dehydrogenation is the rate-determining step for the system under investigation here.This fundamental study of metal-support interactions based on Co growth on the CeO_(2)(110)surface contributes to the understanding of the essence of Co/CeO_(2) catalysts with promising catalytic behavior.It provides theoretical guidance for better designing the optimal Co/CeO_(2) catalyst for tailored catalytic reactions.

Investigation of oxy-fuel combustion for methane and acid gas in a diffusion flame

Co-combustion of methane(CH4)and acid gas(AG)is required to sustain the temperature in Claus reaction furnace.In this study,oxy-fuel combustion of methane and acid gas has been experimentally studied in a diffusion flame.Three equivalence ratios(ER=1.0,1.5,2.0)and CH_(4)-addition ratios(CH_(4)/AG=0.3,0.5,0.7)were examined and the flame was interpreted by analyzing the distributions of the temperature and species concentration along central axial.CH_(4)-AG diffusion flame could be classified into three sections namely initial reaction,oxidation and complex reaction sections.Competitive oxidation of CH_(4)and H_(2)S was noted in the first section wherein H_(2)S was preferred and both were mainly proceeding decomposition and partial oxidation.SO_(2)was formed at oxidation section together with obvious presence of H2 and CO.However,H2 and CO were inclined to be sustained under fuel rich condition in the complex reaction section.Reducing ER and increasing CH4/AG contributed to higher temperature,H_(2)S and CH_(4)oxidation and CO_(2)reactivity.Hence a growing trend for CH_(4)and AG to convert into H_(2),CO and SO_(2)could be witnessed.And this factor enhanced the generation of CS2 and COS in the flame inner core by interactions of CH4 and CO_(2)with sulfur species.COS was formed through the interactions of CO and CO_(2)with sulfur species.The CS_(2)production directly relied on reaction of CH_(4)with sulfur species.The concentration of COS was greater than CS_(2)since CS_(2)was probably inhibited due to the presence of H_(2).COS and CS_(2)could be consumed by further oxidation or other complex reactions.

Methane Emission from Rice Fields:Necessity for Molecular Approach for Mitigation

Anthropogenic methane emissions are a leading cause of the increase in global averagetemperatures,often referred to as global warming.Flooded soils play a significant role in methaneproduction,where the anaerobic conditions promote the production of methane by methanogenicmicroorganisms.Rice fields contribute a considerable portion of agricultural methane emissions,as riceplants provide both factors that enhance and limit methane production.Rice plants harbor both methaneproducingand methane-oxidizing microorganisms.Exudates from rice roots provide source for methaneproduction,while oxygen delivered from the root aerenchyma enhances methane oxidation.Studies haveshown that the diversity of these microorganisms depends on rice cultivars with some genes characterizedas harboring specific groups of microorganisms related to methane emissions.However,there is still aneed for research to determine the balance between methane production and oxidation,as rice plantspossess the ability to regulate net methane production.Various agronomical practices,such as fertilizerand water management,have been employed to mitigate methane emissions.Nevertheless,studiescorrelating agronomic and chemical management of methane with productivity are limited.Moreover,evidences for breeding low-methane-emitting rice varieties are scattered largely due to the absence ofcoordinated breeding programs.Research has indicated that phenotypic characteristics,such as rootbiomass,shoot architecture,and aerenchyma,are highly correlated with methane emissions.This reviewdiscusses available studies that involve the correlation between plant characteristics and methaneemissions.It emphasizes the necessity and importance of breeding low-methane-emitting rice varieties inaddition to existing agronomic,biological,and chemical practices.The review also delves into the idealphenotypic and physiological characteristics of low-methane-emitting rice and potential breeding techniques,drawing from studies conducted with diverse varieties,mutants,and transgenic plants.

Micro segment analysis of supercritical methane thermal-hydraulic performance and pseudo-boiling in a PCHE straight channel

The printed circuit heat exchanger(PCHE) is receiving wide attention as a new kind of compact heat exchanger and is considered as a promising vaporizer in the LNG process. In this paper, a PCHE straight channel in the length of 500 mm is established, with a semicircular cross section in a diameter of 1.2 mm.Numerical simulation is employed to investigate the flow and heat transfer performance of supercritical methane in the channel. The pseudo-boiling theory is adopted and the liquid-like, two-phase-like, and vapor-like regimes are divided for supercritical methane to analyze the heat transfer and flow features.The results are presented in micro segment to show the local convective heat transfer coefficient and pressure drop. It shows that the convective heat transfer coefficient in segments along the channel has a significant peak feature near the pseudo-critical point and a heat transfer deterioration when the average fluid temperature in the segment is higher than the pseudo-critical point. The reason is explained with the generation of vapor-like film near the channel wall that the peak feature related to a nucleateboiling-like state and heat transfer deterioration related to a film-boiling-like state. The effects of parameters, including mass flow rate, pressure, and wall heat flux on flow and heat transfer were analyzed.In calculating of the averaged heat transfer coefficient of the whole channel, the traditional method shows significant deviation and the micro segment weighted average method is adopted. The pressure drop can mainly be affected by the mass flux and pressure and little affected by the wall heat flux. The peak of the convective heat transfer coefficient can only form at high mass flux, low wall heat flux, and near critical pressure, in which condition the nucleate-boiling-like state is easier to appear. Moreover,heat transfer deterioration will always appear, since the supercritical flow will finally develop into a filmboiling-like state. So heat transfer deterioration should be taken seriously in the design and safe operation of vaporizer PCHE. The study of this work clarified the local heat transfer and flow feature of supercritical methane in microchannel and contributed to the deep understanding of supercritical methane flow of the vaporization process in PCHE.

Machine learning-driven optimization of plasma-catalytic dry reforming of methane

This study investigates the dry reformation of methane(DRM)over Ni/Al_(2)O_(3)catalysts in a dielectric barrier discharge(DBD)non-thermal plasma reactor.A novel hybrid machine learning(ML)model is developed to optimize the plasma-catalytic DRM reaction with limited experimental data.To address the non-linear and complex nature of the plasma-catalytic DRM process,the hybrid ML model integrates three well-established algorithms:regression trees,support vector regression,and artificial neural networks.A genetic algorithm(GA)is then used to optimize the hyperparameters of each algorithm within the hybrid ML model.The ML model achieved excellent agreement with the experimental data,demonstrating its efficacy in accurately predicting and optimizing the DRM process.The model was subsequently used to investigate the impact of various operating parameters on the plasma-catalytic DRM performance.We found that the optimal discharge power(20 W),CO_(2)/CH_(4)molar ratio(1.5),and Ni loading(7.8 wt%)resulted in the maximum energy yield at a total flow rate of∼51 mL/min.Furthermore,we investigated the relative significance of each operating parameter on the performance of the plasma-catalytic DRM process.The results show that the total flow rate had the greatest influence on the conversion,with a significance exceeding 35%for each output,while the Ni loading had the least impact on the overall reaction performance.This hybrid model demonstrates a remarkable ability to extract valuable insights from limited datasets,enabling the development and optimization of more efficient and selective plasma-catalytic chemical processes.

Study on the evolution of solid–liquid–gas in multi-scale pore methane in tectonic coal

The rich accumulation of methane(CH_(4))in tectonic coal layers poses a significant obstacle to the safe and efficient extraction of coal seams and coalbed methane.Tectonic coal samples from three geologically complex regions were selected,and the main results obtained by using a variety of research tools,such as physical tests,theoretical analyses,and numerical simulations,are as follows:22.4–62.5 nm is the joint segment of pore volume,and 26.7–100.7 nm is the joint segment of pore specific surface area.In the dynamic gas production process of tectonic coal pore structure,the adsorption method of methane molecules is“solid–liquid adsorption is the mainstay,and solid–gas adsorption coexists”.Methane stored in micropores with a pore size smaller than the jointed range is defined as solid-state pores.Pores within the jointed range,which transition from micropore filling to surface adsorption,are defined as gaseous pores.Pores outside the jointed range,where solid–liquid adsorption occurs,are defined as liquid pores.The evolution of pore structure affects the methane adsorption mode,which provides basic theoretical guidance for the development of coal seam resources.

Extreme massive hydraulic fracturing in deep coalbed methane horizontal wells:A case study of the Linxing Block,eastern Ordos Basin,NW China

Deep coal seams show low permeability,low elastic modulus,high Poisson’s ratio,strong plasticity,high fracture initiation pressure,difficulty in fracture extension,and difficulty in proppants addition.We proposed the concept of large-scale stimulation by fracture network,balanced propagation and effective support of fracture network in fracturing design and developed the extreme massive hydraulic fracturing technique for deep coalbed methane(CBM)horizontal wells.This technique involves massive injection with high pumping rate+high-intensity proppant injection+perforation with equal apertures and limited flow+temporary plugging and diverting fractures+slick water with integrated variable viscosity+graded proppants with multiple sizes.The technique was applied in the pioneering test of a multi-stage fracturing horizontal well in deep CBM of Linxing Block,eastern margin of the Ordos Basin.The injection flow rate is 18 m^(3)/min,proppant intensity is 2.1 m^(3)/m,and fracturing fluid intensity is 16.5 m^(3)/m.After fracturing,a complex fracture network was formed,with an average fracture length of 205 m.The stimulated reservoir volume was 1987×10^(4)m^(3),and the peak gas production rate reached 6.0×10^(4)m^(3)/d,which achieved efficient development of deep CBM.

Ca and Sr co-doping induced oxygen vacancies in 3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts for boosting low-temperature oxidative coupling of methane

It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.

Decorating Single-Atom Catalysts with CO for Efficient Methane Conversion

Direct methane conversion has advantages such as low energy consumption,less processes,and being more economical.However,it is difficult to activate methane at room temperature due to the high dissociation energy of C-H bonds of methane.Additionally,the target products,such as methanol,acetic acid,and other oxygenates,are prone to overoxidation,resulting in the generation of CO_(2).Therefore,the design of catalysts with high activity and selectivity is important.

冻土区土壤甲烷排放的研究进展及发展趋势

作为全球碳循环系统及陆地生态系统的重要组成部分,冻土区土壤甲烷排放在土壤碳库与气候变化之间的反馈联动机制中扮演着关键性角色,并因此成为全球气候变化研究中的前沿热点问题。冻土区土壤甲烷排放的气源主要为微生物产甲烷活动和冻土层、天然气水合物中的气体释放作用,其中,微生物气源的研究较为成熟,而冻土层和天然气水合物气源甲烷的排放研究目前尚停留在定性分析阶段。在影响因子方面,文献计量学统计结果中出现频次最多的关键词依次为土壤温度、湿度和水位条件、有机质含量、地表植被条件等,这些要素可以对甲烷产生、传输和氧化吸收等多个环节产生影响。模型计算法是当前冻土区土壤甲烷排放评估预测的主要方法,包括早期的统计计算模型和近年来出现的基于土壤甲烷排放成因机理的过程模型,相关计算结果有效地支撑了全球气候变化评估研究。通过对冻土区土壤甲烷排放研究成果的梳理和总结,发现当前对冻土区土壤甲烷排放的气源和单因子影响作用认识较为明确,不同尺度的监测和评估方法也较为成熟。但是,对多气源作用下的冻土区土壤甲烷复合排放研究仍然较为薄弱,尤其是在冻土层和天然气水合物的甲烷释放方面,还缺少相关的定量计算研究。与此同时,在影响因子研究方面,也缺少多因素作用下的成因机理和驱动机制分析。因此,可以通过多方法、多因素综合监测研究,利用产甲烷微生物的元基因组分析、多气源土壤甲烷排放的同位素示踪等新技术和新方法,结合卫星遥感等大尺度观测结果,完善冻土区土壤甲烷排放的过程模型。此外,作为全球的“第三极”,青藏高原区域碳循环系统的变化将对亚洲,乃至全球气候变化产生重大影响。因此,还应进一步加强对青藏高原中纬度高原冻土区土壤甲烷排放的相关研究,为区域碳排放的定量评估和全球气候变化的研究提供理论支撑。

甲烷中四氢噻吩气体标准物质制备及应用

目的为天然气加臭剂的测量活动提供可追溯性,以保证检测结果的准确可靠。方法采用称量法研制了摩尔分数为1.00~20.00μmol/mol的甲烷中四氢噻吩气体标准物质,考查了该气体标准物质的均匀性和稳定性。依据该标准物质建立了硫化学发光检测器气相色谱仪(GC-SCD)测定甲烷中四氢噻吩的方法。结果制得的气体标准物质相对扩展不确定度为2%,k=2,国家标准物质证书编号为GBW(E)062460,采用GC-SCD测定甲烷中四氢噻吩的方法,在摩尔分数为0~5.00μmol/mol的范围内,线性良好,相关系数r=1.000,检出限低至0.03μmol/mol,并应用于天然气样品的测试,7次测量的相对标准偏差为2.1%~3.4%。结论基于有证标准物质进行量值溯源的GC-SCD测定甲烷中四氢噻吩的方法准确可靠,为天然气中加臭剂四氢噻吩的测量提供技术保障。

牛舍甲烷浓度监测技术的研究现状及展望

甲烷作为仅次于二氧化碳的全球第二大温室气体,其排放带来的温室效应相当于CO_(2)的25倍,故畜禽排放甲烷浓度增加导致温室效应已越来越受到全球的重视。农业领域畜牧养殖过程中,饲养牛排放甲烷量居多,而牛舍甲烷排放主要来源于牛后肠道排气、打嗝或粪便等有机物无氧分解过程中产生。因甲烷减排是降低全球温室效应的有效途径之一,故对牛舍甲烷监测的准确性是实现甲烷减排的基础。因此,为提高畜牧养殖经济和环境的双重效益,针对国内外牛舍甲烷浓度监测技术的研究情况进行综述。

低浓度甲烷热氧化流向变换反应器的动态行为及余热回收研究

废弃煤矿的低体积分数甲烷(1%-3%)通常被直接排放到大气中,但其较高的升温潜势带来了严重的环境问题。在流向变换反应器中直接热氧化甲烷是一种有吸引力的解决方案,但潜在的爆炸和不稳定燃烧等风险限制了其应用。阐明低含量甲烷在流向变换反应器中热氧化的动力学行为是开发工业级反应器的基础。为此,采用数值模拟的方法分析了低含量甲烷热氧化流向变换反应器的自热操作边界,深入研究了热空气导出量对流向变换反应器行为的影响。结果显示,甲烷体积分数超过0.2%即可实现自热操作;甲烷体积分数从0.5%提升至3.0%,最高床温仍维持在1200℃左右。当甲烷体积分数超过0.5%,可以回收部分热量;相同甲烷含量条件下,最高床温随着热气抽出量的增加而增加;随着甲烷体积分数从0.5%提升到3.0%,允许导出的热空气从12.5%几乎线性地增加到32%。进一步研究发现,以30-50 s的时间间隔反向流动可以确保甲烷的完全转化和床温稳定。上述结果表明,甲烷体积分数在1%-3%时,采用热氧化处理可以实现余热回收;此外,通过调整换向时间和热空气导出量可以实现床层温度控制。

奶牛个体甲烷排放检测装置设计

奶牛个体消化食物过程中的甲烷排放量可作为牧场饲喂管理中优化日粮配方的参考依据。为此,设计了一种基于非分散红外(NDIR)技术的奶牛个体甲烷排放检测装置,采用穿戴式结构和低功耗、无线传输技术,通过双波长差分检测技术,利用比尔朗博定律分析计算甲烷气体的浓度。试验结果表明:装置不影响奶牛的日常活动及采食行为,设计的信号处理电路能够有效减少外部干扰,且响应速度块,通过上位机软件实现对数据实时检测。

井工煤矿甲烷排放精准监测与核算

甲烷作为全球第二大温室气体,具有增温潜势高、寿命短的特点,主要来源于煤炭、油气生产、农业、畜牧业和废弃物处理等领域。积极稳妥有序控制甲烷排放,兼具减缓全球温升的气候效益、能源资源化利用的经济效益、协同控制污染物的环境效益和减少生产事故的安全效益。甲烷也是煤矿生产排放中最主要的温室气体,目前对煤矿甲烷的排放监测及其在煤矿三维立体空间内的浓度分布研究将成为我国甲烷排放控制行动的重点,对煤矿企业更好顺应国家战略具有重要意义。选取山西某高瓦斯矿井、陕西某低瓦斯矿井进行甲烷排放监测核算,以固定监测、手工监测、无人机监测及矿后活动监测等方式研究我国高低瓦斯矿井甲烷分布,并对其甲烷排放量开展分析。结果表明:①美国Climate TRACE网站公布的山西某高瓦斯矿井、陕西某低瓦斯矿井2022年度甲烷排放量与实测法计算的结果差异较大,其中公布的某低瓦斯矿井年度甲烷排放量为实测法计算结果的10.92倍,自上而下的监测核算方法准确性不足,无法为碳交易提供可靠的数据支持。②矿后活动监测核算发现,采用IPCC缺省值计算的矿后活动甲烷排放量是实测法计算的3~5倍,且不同粒径和暴露时间下煤样反馈的矿后活动排放量差异较大。亟需一套统一精准的测试标准,为未来碳市场交易提供公平准确的数据。

非对称泄爆条件下甲烷爆炸双向传播特性的研究

为探究非对称泄爆条件下甲烷爆炸双向传播特性,利用自主搭建的小型爆炸试验系统,对不同点火位置和左端泄爆口面积下甲烷爆炸双侧火焰传播速度和爆炸超压进行了试验研究。结果表明:非对称传播情况下,距离泄爆口较近的右侧火焰的传播速度更快;左端泄爆口面积的减小会进一步促进右侧火焰传播,同时抑制左侧火焰传播,当泄爆口面积小于或等于90mm×90mm时,左侧火焰出现逆流现象;随着左端泄爆口面积的减小,点火源两侧压力、压力差和最大压力上升速率均增大,从而导致爆炸指数增大,提高了爆炸危险性。

甲烷裂解双分散孔催化剂颗粒积碳行为模拟

【目的】为了更好地理解催化剂颗粒的积碳行为,分析积碳效应下催化剂颗粒界面反应传质特性,实现对催化剂颗粒的优化设计与调控。【方法】采用颗粒解析模型,考虑积碳引起的孔隙结构动态演变以及反应性能的衰减,分别探讨单分散孔和双分散孔颗粒积碳形成及所引起的孔隙结构演变规律。【结果】积碳失活从多孔颗粒表层向内部核心移动,扩散主导机制转向反应主导机制;相较于单分散孔颗粒,双分散孔颗粒具备更强的抗积碳性能;固定床反应器中催化剂颗粒分布影响积碳行为,壁面处积碳更加严重,更容易导致失活。【结论】选择双分散孔催化剂颗粒对于积碳行为具有改善作用,同时应选择合适的长径比反应器,削弱壁面效应对积碳行为的影响。

场站空间甲烷逸散泄漏激光遥测光路匹配研究

基于计算流体力学(CFD)对非合作目标条件下甲烷遥测路径进行分析,结合一维视线积分浓度表征模型,开展不同风速、不同泄漏位置工况下甲烷逸散数值模拟研究,探究不同扫描方案下,甲烷视线积分浓度值变化规律,获得油气场站激光检测最优方案,与实际检测路径进行光路匹配。研究结果表明:在不同泄漏位置与不同风速条件下,光路水平距离为5 m的扫描方案能够实现油气场站泄漏气体的快速扫描与报警;随着泄漏位置与检测器水平距离增大,风速增强,光路水平距离为5 m的扫描方案在报警时间方面比其他方案优越性更明显。

不同水分条件下氨基酸添加对温带暗棕壤碳氮含量和甲烷排放的影响

【目的】解析土壤pH值与土壤氮以及CH_(4)排放速率与土壤碳氮含量间的相互关系,为明确碳氮转化及温室气体排放规律、优化温带森林暗棕壤的水分管理提供依据。【方法】以温带森林暗棕壤为研究对象,采用室内培养法,设置水分条件为土壤饱和持水量(WHC)的40%、60%、90%,通过向温带暗棕壤中添加两种不同性质的氨基酸,探讨其对土壤碳氮含量及CH_(4)排放的潜在影响,运用Pearson相关分析法分析土壤碳氮含量、pH值及CH_(4)排放速率间的相关性。【结果】(1)氨基酸处理显著增加了土壤可溶性有机碳(DOC)含量、铵态氮(NH_(4)^(+)-N)含量及CH_(4)排放速率。亮氨酸处理使DOC、NH_(4)^(+)-N含量分别升高21.39%、45.10%,CH_(4)排放速率较CK升高3.20倍,甲硫氨基酸使DOC、NH_(4)^(+)-N含量分别升高21.39%、72.71%,CH_(4)排放速率较CK升高7.00倍;(2)不同氨基酸对土壤硝态氮(NO_(3)^(-)-N)含量的影响存在差异。亮氨酸处理使土壤NO_(3)^(-)-N含量升高了8.41%,但其对于土壤硝化作用的影响可能存在滞后性,而甲硫氨基酸能够显著抑制土壤硝化作用,NO_(3)^(-)-N含量显著降低了37.90%;(3)土壤不同水分条件对土壤DOC、NH_(4)^(+)-N、NO_(3)^(-)-N含量及CH_(4)排放速率均存在显著影响。90%WHC使DOC含量升高11.95%~19.91%,使NH_(4)^(+)-N升高19.83%~35.46%,使NO_(3)^(-)-N降低10.05%~23.79%,使CH_(4)排放速率升高至另外两种水分条件的1.48~2.06倍。60%WHC条件使NH_(4)^(+)-N升高13.05%,使NO_(3)^(-)-N含量升高24.62%。60%WHC可能是温带暗棕壤硝化作用的最适含水量,90%WHC条件有利于DOC积累,同时对NO_(3)^(-)-N的产生存在明显抑制作用;(4)土壤pH与N H4+-N含量呈极显著正相关,与NO_(3)^(-)-N含量呈正相关。CH_(4)排放速率与NO_(3)^(-)-N含量呈极显著负相关,与NH_(4)^(+)-N含量呈负相关,与DOC含量呈极显著正相关。【结论】不同性质氨基酸添加在温带森林暗棕壤碳氮含量及CH_(4)排放中发挥的作用不尽相同。一定范围内,土壤水分含量的升高有利于土壤NH_(4)^(+)-N、NO_(3)^(-)-N、DOC的积累及CH_(4)的排放,但土壤高含水量条件对NO_(3)^(-)-N的产生具有抑制作用。因此,在研究温带森林暗棕壤碳含量、CH_(4)排放及氮转化机制时,建议关注不同氨基酸的差异性作用,同时考虑水分的变化。

温和条件下甲烷提高水合物储氢稳定特性机理

CH_(4)作为促进剂可大幅降低水合物储氢苛刻的热力学条件并提高H_(2)水合物的总储能密度,但目前对CH_(4)提升水合物储氢机理的认识较为缺乏。为此,通过分子动力学模拟研究并建立了CH_(4)/H_(2)双客体分子水合物模型,采用径向分布函数、构象分析和均方位移等方法综合分析了不同温度和压力下水合物结构的稳定性,探究了H_(2)占据孔穴位置、占据比例和水合物热力学稳定性之间的关联,揭示了温和条件下CH_(4)促进水合物储氢的微观机理。研究结果表明:(1)纯H_(2)水合物在严苛条件下笼型结构破损严重,而纯CH_(4)水合物在263~273 K及5~20 MPa温压条件下能稳定存在,说明CH_(4)水合物具备良好的热力学稳定性;(2) 263 K下储氢结构更为稳定,而5^(12)小笼可填充1~2个H_(2)分子,5^(12)6~2大笼中最佳储存3个H_(2)分子,且大笼储氢结构对水合物稳定性影响大,受温度的影响更为敏感。结论认为,CH_(4)/H_(2)水合物储氢体系3L+2S、3L+2L、2S+2S体系在263 K、15~20 MPa温和条件下综合性能较好,其中3L+2S具备最优的热力学稳定性,储氢密度可达0.301%(质量百分比),该研究成果可为水合物储氢技术开发提供理论指导和技术参考。