Modeling the properties of methane + ethane (Propane) binary hydrates,depending on the composition of gas phase state in equilibrium with hydrate

The properties of methane + ethane and methane + propane hydrates of cubic structures sI and sII are theoretically investigated. It is shown that the composition of the formed binary hydrate strongly depends on the percentage of a heavier guest in gas phase. For instance, for a 1% molar ethane concentration in gas phase, even at a low pressure, ethane occupies 60% large cavities in the hydrate sII, and as the pressure grows to 100 atm, it occupies 80% large cavities at a low temperature. The tendency remains the same at a temperature of higher than the ice melting point, but the methane concentration in the hydrate decreases to 30%. In the structure sI, the influence of the component composition of the gas mixture on that of the formed hydrate is less evident. However, in this case, calculation showed also that for a 1% molar ethane concentration in gas phase, ethane molecules occupy from 8 to 10% large hydrate cavities, depending on the pressure. This work is concerned with modeling phase transitions between cubic structures sI and sII of methane + ethane binary hydrates in view of incomplete occupation of cavities in the hydrate by guest molecules. For an ethane concentration under 2% in the gas mixture, the structure sII becomes more thermodynamically stable than the structure sI. However, as the ethane concentration grows to 20% in the equilibrium ice-gas-hydrate and to 40% in the equilibrium water-gas-hydrate, the structure sI becomes more thermodynamically stable. Hence, for low ethane concentrations in a gas mixture, the structure sI can be formed only as a metastable phase. Phase equilibria of methane hydrate sI and mixed methane + propane hydrate sII are considered, depending on the gas phase composition. Similar results are obtained for this equilibrium; this can evidence simultaneous formation of hydrates sI and sII at low propane concentrations.     

Theoretical investigation of structures and compositions of double neon-methane clathrate hydrates,depending on gas phase composition and pressure

The region of existence of neon clathrate hydrates is an actual problem of hydrate chemistry. The current work presents theoretical study of the equilibrium formation conditions of pure neon clathrate hydrates and double clathrate hydrates of neon-methane mixture. The structures and properties of double clathrate hydrates were described within the scope of the previously developed molecular clathrate hydrate model that takes into account the influence of guest molecules on the host lattice, interaction of guest molecules between themselves, and the possibility of multiple filling of host lattice cages by guest molecules. The model makes it possible to find an equilibrium state and thermodynamic properties of clathrate hydrates at given values of p and T. In the present work, we considered the properties of double clathrate hydrates in the range of pressures from 0 to 4 kbar at 250 K. The results of modeling have shown that the mass fraction of neon in double clathrate hydrate of Ne and CH₄ mixture of cubic structure I (sI) can reach 26%, and 22.5% in double hydrate of cubic structure II (sII) even at a low methane concentration (1%) in gas phase, at high pressure. It is shown that in double clathrate hydrates of the Ne and CH₄ mixture at high pressures, phase transition sII-sI can occur.     

天然流体包裹体中甲烷水合物生成条件原位变温拉曼光谱研究

准确获取流体包裹体中气体水合物的生成条件一直是传统包裹体分析方法面临的一个难题。文章采用原位拉曼光谱技术分析了天然流体包裹体中甲烷水合物的生成条件。并由常温拉曼光谱分析表明,研究流体包裹体的流体组成为CH4-H2O体系。通过三种方法控制实验温度的变化,在第三种方法实验条件下获得了-170 ℃时甲烷水合物与冰的拉曼光谱,逐渐升温原位观测甲烷水合物的消失温度。原位拉曼光谱检测结果表明,研究包裹体中甲烷水合物的生成温度为7.5 ℃。结合CH4-H2O体系水合物形成条件相平衡计算,得到包裹体中甲烷水合物生成时的压力为5.587 3 MPa。研究结果表明,原位拉曼光谱技术是准确获取流体包裹体种气体水合物生成条件的一种有效方法。     

显微激光拉曼光谱测定甲烷水合物的水合指数

甲烷水合物是由甲烷气体分子与水分子在低温高压下形成的一种笼型结构化合物,广泛存在于海底陆架区和陆地冻土区,被认为是一种潜在的能源资源。在水合物的晶格中,水分子在氢键的作用下形成大小不同的笼子,甲烷分子可分别进入大笼(51262)和小笼(512)中。在自行研制的实验装置上,分别合成了一系列不同体系下的甲烷水合物,包括十二烷基硫酸钠(SDS)水溶液-甲烷体系、冰粉-甲烷体系以及冰粉-不同粒度砂-甲烷体系。对这些甲烷水合物样品进行了激光拉曼光谱分析,测定了其水合指数,笼占有率等结构参数。结果表明,这些甲烷水合物都为Ⅰ型结构,其水合指数和笼占有率基本不受沉积物粒径大小的影响。在3种体系中生成的水合物,大笼中甲烷分子基本占满,占有率大于97%;小笼中甲烷分子占有率为80%～86%,测得的水合指数为6.05～6.15。     

HFC152a/HCFC141b混合气体水合物相平衡特性研究

1引言气体水合可使水在8—12”C络合结晶形成水合物，同时释放反应热（蓄冷）。其反应热与传热性能均较理想，被认为是理想的空调蓄冷介质山。早期研究的主要是Rll和R12的水合物。由于Rll和R12严重破坏大气臭氧层而受控，因此寻找替代CFC的新型致冷剂气体水合物成为当前的研究重点［‘－‘］。近年来我们根据混合物性能互补原理，提出了利用混合气体水合物构造性能优良的蓄冷材料的设想［‘1。HFC152a和HCFC141b分别是R12和Rll的首选替代物之一。HFC152a是较活跃的致水合物质，但相变温度和压力偏高。而HCFC141b水合物的相变温度…     

碳化铝与水反应合成甲烷水合物的实验研究

 利用自行设计的高压气水合物实验装置,通过碳化铝与水反应成功合成了甲烷水合物。实验结果表明,碳化铝与水反应合成甲烷水合物的方法有效地解决了传统甲烷水合物模拟实验中甲烷气体引入问题;同时,碳化铝与水反应产生的甲烷及沉淀物能较好地模拟海洋环境中水合物形成的自然条件,为实验模拟甲烷水合物研究提供了一种新方法。利用此方法,对甲烷水合物合成与分解温度、压力条件及动力学过程进行了初步研究。     

显微激光拉曼光谱原位观测甲烷水合物生成与分解的微观过程

采用显微激光拉曼光谱技术对高压透明毛细管中甲烷水合物的生成与分解的微观过程进行了原位观测,初步探讨了甲烷水合物笼型结构的变化规律.结果表明,甲烷水合物在生成过程中,甲烷分子的拉曼峰(2 917 cm-1)逐渐分裂为两个峰(2 905和2 915 cm-1),表明溶解态甲烷分子从单一的化学环境进入了两个有差异的化学环境中...     

甲烷水合物的固体核磁共振碳谱与激光拉曼光谱研究

甲烷水合物（CH₄·nH₂O）是主要由甲烷和水分子构成的冰状笼型化合物,在自然界储量巨大．固体核磁共振（NMR）波谱和激光拉曼光谱是在分子水平分析甲烷水合物的重要手段．该文利用低温固体核磁共振碳谱（¹³C NMR）对合成的甲烷水合物结构进行了研究,分别使用¹³C交叉极化（¹³C CP）和高功率质子去偶（¹H HPDEC）2种脉冲程序采集甲烷水合物的¹³C NMR谱图,结合实验结果分析及理论推导可知,使用¹H HPDEC方法得到的¹³C NMR谱图信号更强,更利于定量分析;甲烷气体与冰粉合成的甲烷水合物为I型,其大笼和小笼占有率分别为0.988和0.824,水合数为6.07;甲烷气体与SH2站位沉积物和冰粉合成的甲烷水合物也为I型,其大笼和小笼占有率分别为0.987和0.887,水合数为5.98;SH2站位沉积物使合成的甲烷水合物的小笼占有率提高、水合数降低、水合物饱和度提高．激光拉曼光谱结果证实了上述结果的准确性．该文为甲烷水合物测试提供了重要的方法参考．     

Methane combustion in hydrate systems: Water-methane and water-methane-isopropanol

Kinetics of dissociation of synthetic and natural methane gas hydrates, and also double isopropanol-methane hydrate is investigated. Thermal fields of the sample surfaces are measured by means of thermal imaging in combustion of released methane with clathrate dissociation. The dissociation rates of natural hydrate and double hydrate with isopropanol are many times lower than those of synthetic methane hydrate. Methane combustion is accompanied by formation of a thin water film on the powder surface, which has a strong effect on the heat and mass transfer mechanisms. The experiments demonstrated partial self-preservation for methane hydrate and the absence of self-preservation for double isopropanol-methane hydrate. The experimentally observed dissociation rate of double isopropanol-methane hydrate is considerably lower than that of methane hydrate.     

激光拉曼光谱在气体水合物研究中的应用

天然气水合物是一种重要的潜在能源。用激光拉曼光谱法表征气体水合物能够为研究水合物形成机理和开采方法提供重要信息。系统介绍了激光拉曼光谱法的基本原理,综述了激光拉曼光谱仪在气体水合物微观表征上的各种实际应用。通过激光拉曼测试可分析水合物气体组成、推测结构类型,再利用经验公式或者相对定量法可计算出其大/小笼的气体占有率和水合数;利用原位拉曼技术可以观测水合物形成和分解的微观过程,解析气体分子进入和离开笼子的进程、进行水合物形成和分解过程中气体浓度变化及水合物形成过程中气体溶解度的测定,辨识水合物系统中的相变过程,进而研究水合物形成和分解动力学;激光拉曼光谱法还可用于研究超高压条件下气体水合物的结构及其变化过程。原位拉曼光谱能够对深海天然气水合物及其环境在原位进行表征;利用拉曼成像技术可以对水合物晶体表面进行系统测定,探求气体组分在晶体表面的分布。随着激光拉曼技术的发展及与其他设备联用水平的提高,激光拉曼光谱仪向便携,高灵敏度发展,能够更广泛深入地进行气体水合物微观研究。     

二氧化碳-甲烷混合气体水合物四相区实验研究

以水合物的形式封存CO₂和置换海底的天然气（CH₄）水合物需要对CO₂-CH₄混合水合物的四相平衡状态及数据有清楚的了解。本文通过实验和模型计算对不同组分的CO₂-CH₄混合水合物的较高四相区（Q2）相平衡进行了测定和表述。实验温度范围为273.16～297 15 K,压力范围分为0～10 MPa。四相区的温度压力范围分别是283.51到287.04 K和4.74到8.37 MPa,甲烷的摩尔组份为0～0.225。结果揭示了相平衡温度和压力随着甲烷组分而变化情况以及四相区的范围和临界点,同时还给出了CO₂-CH₄混合气体水合物在四相状态下的融化开始和融化结束点。实验结果与热力学模型计算得出的CO₂-CH₄混合气体水合物相平衡结果进行比较,两者很好吻合,四相平衡区域的存在范围得以明确。     

基于Raman光谱技术的瓦斯混合气水合过程定量分析

瓦斯水合物微观晶体结构研究对水合分离技术具有重要理论意义。利用Raman光谱技术对三种含高浓度CO₂瓦斯混合气水合反应过程进行在线观测,并对水合物相Raman光谱图进行分析,获取了瓦斯水合物不同生长阶段大、小孔穴占有率,同时利用van der Waals与Platteeuw热力学统计模型间接获得水合指数等晶体结构信息。结果表明,瓦斯水合物孔穴占有率及水合指数在水合物不同生长阶段未发生较大变化,水合物相中大孔穴几乎被客体分子填满,CO₂与CH₄分子共同占据大孔穴,但CO₂占绝大多数,达到78.58%~94.09%,CH₄分子仅为4.52%~19.12%,这主要是由于两种分子间存在竞争关系且气样中CO₂浓度明显高于CH₄,大孔穴占有率维持在97.70%~98.68%;小孔穴占有率为17.93%~82.41%,占有率普遍偏低,且仅有CH₄分子;随气样中CH₄浓度增加,CH₄在大、小孔穴中的占有率均有所增加,且CH₄分子在大孔穴中的占有率均明显低于在小孔穴中占有率;水合物生长不同阶段水合指数为6.13~7.33,随气样中CH₄浓度的增加,小孔穴占有率有所增加,致使水合指数随之降低;由于瓦斯水合物生长分布不均匀,三种气样对应的不同生长阶段水合指数均呈不规则变化。     

Structural changes in gas hydrates and existence of a filled ice structure of methane hydrate above 40 GPa

Recent studies have contributed a great deal to our understanding of the structural changes in gas hydrates under pressure. A feature of structural changes in terms of pressure and guest size is summarised in the former part of this paper. The gas hydrate with the guest size from argon to methane finally take a common filled ice I_h structure, although they have different initial and intermediate structures. In the latter part, retention of the filled ice I_h structure of methane hydrate up to 42 GPa is described. In situ X-ray diffractometry and optical observation revealed the existence of the filled ice structure with the volume change of 40% and large anisotropic compressibility. The distances between oxygen atoms estimated from the unit cell parameters suggested that symmetrization of hydrogen bonds occurred in the structure.     

Density functional theory study of structural stability for gas hydrate

Using the first-principles method based on the density functional theory(DFT),the structures and electronic properties of different gas hydrates(CO_2,CO,CH_4,and H_2) are investigated within the generalized gradient approximation.The structural stability of methane hydrate is studied in this paper.The results show that the carbon dioxide hydrate is more stable than the other three gas hydrates and its binding energy is-2.36 e V,and that the hydrogen hydrate is less stable and the binding energy is-0.36 e V.Water cages experience repulsion from inner gas molecules,which makes the hydrate structure more stable.Comparing the electronic properties of two kinds of water cages,the energy region of the hydrate with methane is low and the peak is close to the left,indicating that the existence of methane increases the stability of the hydrate structure.Comparing the methane molecule in water cages and a single methane molecule,the energy of electron distribution area of the former is low,showing that the filling of methane enhances the stability of hydrate structure.     

Clathrate hydrates: recent advances on CH4 and CO2 hydrates,and possible new frontiers

Gas hydrates continue to attract enormous attention throughout the energy industry, as both a hindrance in conventional production and a substantial unconventional resource. Scientists continue to be fascinated by the hydrates’ ability of sequestering large amounts of hydrophobic gases, unusual thermal transport properties and unique molecular structures. Technologically, clathrate hydrates promise advantages in applications as diverse as carbon sequestration and water desalination. The communities interested in hydrates span traditional academic disciplines, including earth science, physical chemistry and petroleum engineering. The studies on this field are equally diverse, including field expeditions to attempt the production of natural gas from hydrate deposits accumulated naturally on the seafloor, to lab-scale studies to exchange CO₂ for CH₄ in hydrates; from theoretical studies to understand the stability of hydrates depending on the guest molecules, to molecular simulations probing nucleation mechanisms. This review highlights a few fundamental questions, with focus on knowledge gaps representing some of the barriers that must be addressed to enable growth in the practical applications of hydrate technology, including natural gas storage, water desalination, CO₂ – CH₄ exchange in hydrate deposits and prevention of hydrate plugs in conventional energy transportation.     

Coupled combustion of mixture in hydrogen generation

The specifics of the combustion of micron-sized flaky aluminum powder in mixtures with crystal-line hydrates over a wide pressure range at various mass ratios between aluminum and crystalline hydrate are studied. Limiting conditions of combustion of mixtures regarding the composition and pressure are determined. With use of a stoichiometric mixture of aluminum with sodium sulfate crystalline hydrate, the coupled combustion composite samples with additional oxidants, ammonium nitrate and potassium nitrate, and samples with spread oxidant is examined. It is established that the velocity of coupled combustion can significantly exceed the velocity of combustion of the base mixture. Limiting conditions for combustion of mixtures are determined.     

甲烷水合物形成促进技术实验研究

实验研究了液态烃(环戊烷和甲基环己烷)对甲烷水合物形成条件的影响,测试结果表明液态烃降低了甲烷水合物的形成压力,并改变了形成水合物的结构。实验研究了促进剂(液态烃和表面活性剂)对水合物形成诱导时间和生长过程的影响,结果表明液态烃和表面活性剂降低了水合物形成的诱导时间,提高了水合物形成速度;而且表面活性剂提高了水合物形成过程中的耗气量,并改变了水合物形成机理。     

Boiling-up of liquid nitrogen jet in water

The hydrodynamic processes occurring at injection of cryogenic liquid into water pool were studied experimentally. Processes accompanying the phase transitions were registered. Data testify the developing pressure burst with an amplitude sufficient for possible formation of gas hydrates when methane is injected as a cryogenic fluid.     

Explosive boiling of liquid nitrogen jet in water

The hydrodynamic processes occurring at injection of cryogenic liquid into water pool were studied experimentally. The processes accompanying phase transitions were registered. Data testify the developing pressure drops of the amplitude within a range sufficient for possible formation of gas hydrates with application of methane as the injected cryogenic liquid.     

混合制冷剂气体水合物生成及融解过程实验研究

1引言城市建筑物中，空调作为最大用电设备之一，夏季占建筑物耗电总量的一半以上，为了缓解高峰用电负荷并有效利用低谷电力，解决峰期用电紧张的矛盾，达到总体节能的目的，空调蓄冷移峰节电技术被认为是实现城市供电平衡和建筑节能的重要手段。作为实用的空调蓄冷技术，最为重要的是其蓄冷材料的相变温度与空调工况相适应，即在5～12℃发生相变，且相变潜热大，传热性能好．氟里昂气体水合物作为蓄冷材料，具有适合空调储冷的理想性质，可使水在8～12℃水合结晶，形成暖冰时释放反应热，其反应热与结冰潜热相当[1]。然而，由于一些氟里昂…