CO_2/CH_4在干酪根中竞争吸附规律的分子模拟

选取有机质作为研究对象,构建干酪根模型,采用巨正则系综蒙特卡罗(GCMC)方法和分子动力学方法(MD)研究不同摩尔分数、不同压力下CH_4和CO_2的气体的竞争吸附行为以及吸附引起的干酪根本体形变。结果表明:CH_4和CO_2单组分吸附时吸附量随着压力的增大而增大,CO_2吸附会在较小的压力时达到饱和,两种气体吸附符合Langmuir吸附规律,可以使用Langmuir方程进行拟合;在相同的压力和温度下,CO_2/CH_4吸附选择性会随着CO_2摩尔分数的增大而减小,CO_2更易被干酪根吸附;干酪根与CO_2有较强的相互作用,干酪根中不同的原子对吸附起着不同的作用;低压阶段吸附是引起体积应变的主要原因,高压阶段压力对体积应变发挥明显作用。     

Lattice-Boltzmann simulation of microscale CH4 flow in porous rock subject to force-induced deformation

Accurate knowledge of the influence of rock deformation on the permeability of fluid flow is of great significance to a variety of engineering applications, such as simultaneous extraction of coal and gas, oil/gas exploitation, CO2 geological sequestration, and under- ground water conservation. Based on the CT representation of pore structures of sandstones, a LBM （Lattice Boltz- mann Method） for simulating CH4 flOW in pore spaces at microscale levels and a parallel LBM algorithm for large- size porous models are developed in this paper. The properties of CH4 flow in porous sandstones and the effects of pore structure are investigated using LBM. The simu- lation is validated by comparing the results with the mea- sured data. In addition, we incorporate LBM and FEM to probe the deformation of microstructures due to applied triaxial forces and its influence on the properties of CH4 flow. It is shown that the proposed method is capable of visually and quantitatively describing the characteristics of microstructure, spatial distribution of flow velocity of CH4,permeability, and the influences of deformation of pore spaces on these quantities as well. It is shown that there is a good consistency between LBM simulation and experi- mental measurement in terms of the permeability of sandstone with various porosities.     

小尺度管道中CH4-O2爆炸火焰传播规律实验研究

为研究小尺度管道中CH₄-O₂爆炸火焰传播规律,设计并建立了小尺度管道实验系统,由小尺度管道、配气系统、点火系统、爆炸压力数据采集系统、高速摄影系统以及数据处理系统等组成. 利用小尺度管道实验系统,研究了不同初始压力、不同初始浓度条件下CH₄-O₂混合气体爆炸火焰传播的规律. 爆炸火焰传播速度由高速摄影系统采集的图像利用Matlab程序进行处理并计算得到. 结果表明:同一初始浓度条件下,随着初始压力的增加,爆炸火焰在管道中传播的最大速度随之增大;管道中爆炸火焰最大速度与初始压力的倒数近似呈线性关系;对于不同初始浓度下的混合气体,都存在使混合气体形成加速火焰的最低初始压力;以化学当量浓度（CH₄+2O₂）为界限,当初始浓度越接近化学当量浓度时,混合气体形成加速火焰所需的最低初始压力越小.      

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

Hydrogen Adsorption on Metal-Organic Framework MOF-177

This review summarizes the recent literature on the synthesis, characterization, and adsorption properties of meal-organic framework MOF-177. MOF-177 is a porous crystalline material that consists of Zn4O tetrahedrons connected with benzene tribenzoate (BTB) ligands. It is an ideal adsorbent with an exceptionally high specific surface area (BET4500 m2/g), a uniform micropore size distribution with a median pore diameter of 12.7 ?, a large pore volume (2.65 cm3/g), and very promising adsorption properties for hydrogen storage and other gas separation and purification applications. A hydrogen adsorption amount of 19.6 wt.% on MOF-177 at 77 K and 100 bar was observed, and a CO2 uptake of 35 mmol/g on MOF-177 was measured at 45 bar and an ambient temperature. Other hydrogen properties (kinetics and heat of adsorption) along with adsorption of other gases including CO2, CO, CH4, and N2O on MOF-177 were also be discussed. It was observed in experiments that MOF-177 adsorbent tends to degrade or decompose when it is exposed to moisture. Thermogravimetric analysis showed that the structure of MOF-177 remains intact at temperatures below 330℃ under a flow of oxygen, but decomposes to zinc oxide at 420℃.     

挥发性油藏酸气回注的最小混相压力与组分优化

高含H_2S和CO_2酸性气体的低渗透挥发性油藏在开发过程中,H_2S和CO_2会以溶解气的形式被采出,并占有较高的摩尔分数。分离器条件下的气态轻烃通过回注地层,在油藏压力高于最小混相压力(MMP)时达到混相驱动,一方面可以显著提高驱油效率,另一方面可以起到减缓压力衰竭的目的。H_2S和CO_2作为污染气体,分离和回收成本较高;而与烃气一同回注地层势必会对MMP产生影响。因此,需要研究酸性气体对溶解气回注MMP的影响规律并且合理地优化回注气组分。在对目标区块原油组分拟合重组的基础上,通过混合单元格法预测MMP,研究了溶解气主要组分的混相能力以及H_2S和CO_2对烃气驱MMP的影响规律,通过正交试验方法优化了注入气比例。结果表明:作为酸性杂质气体H_2S和CO_2具有较强的混相能力,可以降低注气MMP;最优注气形式为溶解气直接回注地层。     

Effect of elevated CO2 on CH4 emission

Global CH₄ emission may increase under CO₂ enrichment condition, which is projected for the future. CO₂ enrichment could affect CH₄ emission in two ways: (i) Photosynthesis of plants that also include plants in rice paddies and natural wetlands will be stimulated under CO₂ enrichment condition. CH₄ emission rate may be increased due to the accumulation of more plant biomass, root exudes and soil organic matters. (ii) Combined with other global warming forces, CO₂ enrichment may bring a change of atmospheric temperature and precipitation around the world. CH₄ emission will also be changed with the variation of the area and distribution of rice paddies and natural wetlands.     

不同注源气体置换-驱替煤层甲烷突破时间的差异性分析

煤层注气促抽瓦斯是近年来逐步发展起来的强化抽采技术,注气突破时间是该技术的重要参数之一。突破时间是指注源气体从煤层一端注入到另一端检测出该组分所需的时间,它与注源气体的吸附性、渗透性有着密切的关系。为了研究渗透和吸附对注气突破时间的影响规律,利用含瓦斯煤层注气模拟实验装置,进行了煤层注He,N_2和CO_2置换-驱替CH_4的实验室模拟实验。实验结果表明,不考虑煤对气体吸附性的纯渗流条件下,N_2和CO_2纯渗流突破时间极短,仅为总突破时间的5.93%和0.28%,表明气体吸附性能是引起总突破时间差异的主要因素;另外,随着注源气体吸附性增强,其总突破时间大幅度增加,He,N_2和CO_2的总突破时间分别为0.92,14,246 min。实验结果结合理论模型计算分析得出:注源气体吸附性越强,总突破时间越长,注气初期的置换效应越明显,但随着注源气体的吸附不断趋于饱和,其驱替效应逐渐增强。     

注超临界CO_2开采高温废弃气藏地热机制与采热能力分析

高温废弃气藏具有巨大的地热开采潜力。在对比分析超临界CO2和常规携热介质水的热物性基础上,提出注超临界CO2开采高温废弃气藏地热的方法。利用数值模拟方法对CO2在高温废弃气藏中的采热能力及影响因素进行评估。结果表明,由于CO2具有很高的可注性和流动性,超临界CO2的采热速率可达到水的1.5倍;利用CO2循环开采高温气藏地热,不仅可以实现高效地热开发,还可以实现CO2地质埋存;对废弃气藏而言,可以充分利用现有井网和地面设施,减少初期资本投入,实现高温废弃气藏地热的有效和经济开发,进一步提高气藏的利用价值,延长其经济寿命。     

CO<Subscript>2</Subscript> gas emplacement age in the Songliao Basin: Insight from volcanic quartz <Superscript>40</Superscript>Ar-<Superscript>39</Superscript>Ar stepwise crushing

Due to a lack of suitable minerals, the gas/oil emplacement ages have never been accurately obtained before. CH₄-CO₂-saline- bearing secondary inclusions are found in quartz from the volcanic rocks of the Yingcheng Formation, the container rocks of the deep CO₂ gas reservoir in the Songliao Basin. The inclusion fluid was trapped into microcracks in quartz during the gas emplacement and accumulation, providing an optimal target for the ⁴⁰Ar-³⁹Ar stepwise crushing technique to determine the CO₂ gas emplacement age. ⁴⁰Ar-³⁹Ar dating results of a quartz sample by stepwise crushing yield a highly linear-regression isochron with an age of 78.4±1.3 Ma, indicating that the accumulation of the deep CO₂ gas reservoir in the Songliao Basin occurred in the late Cretaceous. This is the first time to report an exact isotopic age for a CO₂ gas reservoir, which indicates that the ⁴⁰Ar-³⁹Ar dating can serve as a new technique to date the oil/gas emplacement ages.     

Fluxes of CO2, N2O and CH4 from a typical temperate grassland in Inner Mongolia and its daily variation

Using a dark enclosed chamber technique, the fluxes of CO₂, N₂O and CH₄ from nature and disturbed grassland were measured on the spot in Inner Mongolian Temperate Grassland along the annual rainfall gradient section ranging from 450 to 200 mm. The results showed that the measured mean fluxes of CO₂, N₂O and CH₄ were (1 180.4 ± 308.7), (0.010 ± 0.004) and (−0.039 ± 0.016) mg · m⁻²/h, respectively. The decrease of the fluxes of CO₂, N₂O and CH₄ follows with that of annual rainfall gradient in the measurement area. Human activities, such as grazing and reclamation are also critical factors to affect the fluxes of these gases from grassland. Daily continuous measurement of CO₂, N₂O and CH₄ fluxes showed a strong diurnal variation with higher emission in the daytime. A good relationship between the fluxes of CO₂, N₂O, CH₄ and temperature was exposed in this study.     

Preferential Oxidation of CO in a Hydrogen-Rich Gas Through Au/NaY Catalytic Membranes

This paper describes novel Au/NaY catalytic membranes for preferential oxidation of CO (CO-PROX) in an H2-rich gas. NaY zeolite membranes with a high CO2/N2 separation factor were loaded with nanosized Au particles using an ion-exchanged method. X-ray diffraction analyses showed that the structure of the NaY zeolite was not damaged by the ion exchange process. CO-PROX experiments showed that the catalytic membranes had excellent catalytic performance for selective oxidation of CO. The CO/H2 molar ratio on the permeate side decreased with increasing operating temperature in the range of 80-200℃. At 200℃, almost no CO was detected from the permeate stream of a catalytic membrane with the feed con-taining 0.67% CO, 1.33% O2, 32.67% H2, and He in balance. Thus, these Au/NaY catalytic membranes show a promise for CO removal from hydrogen fuels.     

致密油储层CO2驱核磁共振实验研究

针对致密油储层动用困难问题本研究以CO_2为注入介质,对致密油注气开发效果进行评价,并借助核磁共振技术,从微观角度阐述了致密油储层注CO_2的驱替特征。实验结果表明,CO_2驱可以有效启动赋存在致密孔隙中的原油,非混相压力下(10 MPa),CO_2突破快,小孔隙中原油未动用,驱替后原油饱和度分布不均匀,驱替效率低;而在混相压力之上(24 MPa),CO_2突破明显变慢,驱替后原油饱和度均匀下降,大小孔隙中的原油均被启动,采出程度较高。此外从采出原油组成可以看出,高压下CO_2抽提作用非常明显,原油组分以C7~C29为主,几乎不合C30+组分,这表明CO_2会导致原油中重质组分在孔隙中沉积。     

三峡水库不同运行工况下中段干流碳源气体释放通量研究

来自陆地大量有机碳源的输入,以及三峡库区调度运行和筑坝蓄水导致CO_2、CH_4等碳源气体的排放成为近来关注的热点。以三峡库区干流中段为研究对象,于2017年8月—2018年11月对忠县(ZX),万州(WZ),涪陵(FL)进行每月采样分析,探求水-气界面CO_2、CH_4通量在水库不同运行工况下的变化特征。研究发现,在观测期间内,ZX采样点CO_2浓度在0.008 6～0.115 3 mmol/L波动,WZ采样点CO_2浓度在0.003 5～0.116 8 mmol/L波动,FL采样点0.006 3～0.098 6 mmol/L,整体上3个采样点的CO_2浓度变化趋于一致,都在库区泄水期运行4—5月CO_2浓度达到峰值,在低水位运行期的6—9月降到最低值。CH_4通量在水库低水位运行期表现为"汇",FL点位在泄水期达到"源"的最大值;3个采样点的CO_2通量在泄水期均表现为"源"的特征,低水位运行期的CO_2通量表现为"源"与"汇"的转换。通过与国外已有水库监测数据比较分析,CO_2扩散通量在全球水库序列中处于中等水平,CH_4扩散通量在全球水库序列中处于中等偏下水平。     

明胶膜醇／水渗透汽化性能的研究

用牛骨胶制备明胶膜,用于乙醇/水混合物的渗透汽化分离研究,结果表明,该膜在常温下分离85％乙醇时运行3h便可到达稳定操作状态;料液中醇含量增大、膜的分离系数提高但通量下降;而温度升高或汽相侧真空度提高都能导致膜通量与分离系数的同时提高。     

Zr-pillared montmoril lonite supported cobalt nanoparticles for Fischer – Tropsch synthesis

In this article Fischer–Tropsch(FT) synthesis was studied over cobalt nanoparticles supported on modifed Montmorillonite(Zr-PILC).Co-loaded/Zr-PILC catalysts were synthesized by hydrothermal methods and were characterized by XRD,XRF,BET,H2-TPR,TGA and SEM techniques.FT reactions were carried out in fxed bed microreactor(T 225 1C,260 1C and 275 1C,P 1,5 and 10 bars).The FT-products obtained over Co-loaded/Zr-PILC catalysts showed increased selectivity of C2–C12hydrocarbons and decreased selectivity towards CH4and higher molecular weight hydrocarbons(C21) at a TOS of 2–30 h as compared to the Co-loaded/NaMMT catalysts.With increase in reaction temperature from225 1C to 275 1C,CO-conversion and CH4selectivity increases while that of C5+hydrocarbons decreases.Decrease in CH4selectivity while increase in C5+hydrocarbons and CO-conversion were observed on increasing the pressure of reaction.     

Reactive ion etching of poly(vinylidene fluoride-trifluoroethylene) copolymer for flexible piezoelectric devices

A microfabrication process for poly(vinylidene fluoride-trifluoroethylene)(P(VDF-TrFE)) based flexible piezoelectric devices is proposed using heat controlled spin coating and reactive ion etching(RIE) techniques.Dry etching of P(VDF-TrFE) in CF 4 +O2 plasma is found to be more effective than that using SF 6 +O2 or Ar+O2 feed gas with the same radiofrequency power and pressure conditions.A maximum etching rate of 400 nm/min is obtained using the CF 4 +O2 plasma with an oxygen concentration of 60% at an antenna power of 200 W and a platen power of 20 W.The oxygen atoms and fluorine atoms are found to be responsible for the chemical etching process.Microstructuring of P(VDF-TrFE) with a feature size of 10 m is achieved and the patterned films show a high remanent polarization of 63.6mC/m 2.     

植物绝缘油击穿放电故障特征气体分析

对山茶籽植物绝缘油和矿物绝缘油两种变压器用油进行击穿放电故障试验,采用油中溶解气体分析方法测量并分析两种绝缘油放电故障所产生的油中溶解气体,分析并对比两种绝缘油纯油及油纸击穿产生气体的种类及百分含量。结果表明:两种绝缘油在击穿故障后均产生H_2、CH_4、C_2H_4、C_2H_6、C_2H_2、CO及CO_2这7种特征气体;随击穿故障次数的增加,植物绝缘油中溶解气体总量呈增加趋势,并且山茶籽植物绝缘油中CO和CO_2溶解气体含量大于矿物绝缘油;在两种绝缘油中,C_2H_2的含量在总烃中始终是最高的,这说明与矿物油相同,C_2H_2是山茶籽植物绝缘油电击穿故障的主要特征气体。     

特低渗透油藏CO2非混相驱井距与产量关系研究

井距是新井井位部署及老井井位调整的关键因素,井距与产量相关;对特低渗透油藏CO_2非混相驱井距与产量关系的研究很少。在经典油气两相渗流理论的基础上,考虑CO_2溶解于原油所产生的降黏作用及油相启动压力梯度,建立了一个一维油气两相渗流数学模型。基于Buckley-Leverett非活塞驱替理论对饱和度方程进行求解,开发了井距计算软件,分析了生产压差、CO_2驱替前缘推进距离百分比、渗透率对井距与产量关系的影响。计算结果显示,产量越大,井距越小,井距变化的幅度也越小。在注气井近井带,油相黏度由1.5 m Pa·s降低到0.4 m Pa·s;在生产井近井带,油相黏度由1.5 m Pa·s降低到0.6 m Pa·s,CO_2对于原油的降黏幅度可以达到70%左右,从注气井到生产井,油相黏度逐渐升高。为特低渗透油藏CO_2非混相驱井距与产量关系研究提供了一种计算方法,绘制了井距与产量随不同参数变化的理论图版,方便油田应用。     

尿素辅助模板法合成介孔氮掺杂CeO2及其CO2捕获应用研究

以硝酸铈为前驱物,以尿素为助剂,采用一种简单的模板法合成了介孔氮掺杂CeO₂材料.利用X射线衍射仪(XRD)、吸附-脱附仪(BET)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FT-IR)等设备对合成材料进行表征.多种测试结果证明:试验得到的纳米材料具有均一的介孔结构和较高的比表面积(124.8 m²·g^-1)并掺杂了氮元素.同时,测定了介孔CeO₂材料对于CO₂的吸附性能,并研究了氮掺杂对CeO₂材料的CO₂吸附性能的影响.结果表明:相比未掺杂氮的介孔CeO₂,氮掺杂的介孔CeO₂具有更好的CO₂吸附性能和循环吸附脱附性能.