天然气水合物研究进展

本文介绍了天然气水合物研究的历史和现状, 天然气水合物的结构, 它在冻土地带和海洋底部地表层的形成过程, 它对石油天然气工业的影响以及抑制生成天然气水合物的方法。介绍了天然气水合物作为潜在能源的巨大优势以及它对地球气候变化--温室效应的潜在危险性。     

天然气水合物浆体分解对其在垂直管中流动特性影响的研究

针对天然气水合物浆体开采提升过程中水合物分解的问题,采用Euler多相流模型以及Finite-Rate/Eddy-Dissipation模型对天然气水合物浆体垂直管输的固-液两相流动以及气-液-固三相流流动特性进行研究。结果表明,受天然气水合物分解产生的气体影响,天然气水合物颗粒的速度分布、体积浓度分布均随高度的变化呈现出波动-均匀-波动的规律;水合物分解对浆体管道运输具有减阻作用,并提出天然气水合物浆体分解工况下,其流动速度不应低于3m·s~(-1);通过对管道的阻力特性分析,拟合出水合物分解下的水力提升阻力损失与流速的关系式,为天然气水合物浆体管道的经济提升参数提供指导。     

基于量子化学计算方法的天然气水合物稳定性研究进展

天然气水合物以资源丰富、优质、洁净等特点,被视为21世纪新能源。天然气水合物稳定性的研究对天然气水合物资源勘探开发具有重要意义。本文简述了微观、介观、宏观、矿藏四个尺度天然气水合物稳定性的研究,重点从微观量子尺度介绍了量子化学计算方法对水合物晶体结构及其稳定性以及水合物宏观物理特性微观表征的计算研究。应用量子化学计算方法可以对天然气水合物的晶体结构、电子轨道分布、振动光谱、成键特性及主客体相互作用进行计算研究,其结果能够为天然气水合物在油气储运、水合物成藏、开采及其综合利用等方面的研究提供理论支持。目前,量子化学计算方法的优化与分子动力学模拟、分子力学模拟等方法的结合将有助于水合物形成和分解微观机理研究的发展,提升计算精度和扩大研究体系,为矿场尺度的天然气水合物资源开采利用提供理论支持。     

天然气水合物合成与分解模拟实验研究与设计

针对大学化学中有关天然气水合物的内容,设计了天然气水合物的教学实验和模拟实验装置,实现了天然气水合物在不同实验条件下的合成与分解等多个实验。仪器操作简单,实验可重复性高,可通过多种方式判断水合物是否生成或分解。     

天然气水合物抑制剂用高分子研究进展

海底天然气开采过程中,甲烷和水可以形成天然气水合物,阻塞油气管道。本文先简要介绍高分子化合物用于水合物抑制剂的发展过程,从抗冻抑制剂的结构与性能关系,探讨了高分子型的低剂量天然气水合物抑制剂的特性、作用机理和主要影响因素。近年来的研究发现在寒冷地区海洋鱼类和昆虫体内存在一些抗冻蛋白,不仅能够降低水的冰点,而且能抑制天然气水合物的形成,是绿色环保的天然抑制剂,模拟这些具有抗冻性能的蛋白质结构的高分子化合物为今后水合物抑制剂研究提供一个新的发展方向。本文还提出了今后值得开展研究和应用的若干问题。     

南海神狐海域及祁连山冻土区天然气水合物的拉曼光谱特征

采用显微激光拉曼光谱对我国在南海神狐海域及祁连山冻土区首次钻获的天然气水合物实物样品进行了详细的研究, 探讨了其笼型结构特征及其气体组成. 结果表明, 南海神狐海域天然气水合物样品是典型的I型结构(sI)水合物, 气体组分主要是甲烷, 占99%以上; 水合物大笼的甲烷占有率大于99%, 小笼为86%, 水合指数为5.99. 祁连山冻土区天然气水合物气体组分相对复杂, 主要成分除甲烷外(70%左右), 还有相当数量的乙烷、丙烷及丁烷等烃类气体, 从拉曼谱图上可初步判断其为II型结构(sII)水合物; 水合物的小、大笼的甲烷占有率的比值(θ_S/θ_L)为26.38, 远远大于南海神弧海域水合物的0.87, 这主要是由于祁连山水合物气体组分中的大分子(乙烷、丙烷及丁烷等)优先占据水合物的大笼, 大大减少了大笼中甲烷分子的数量.     

钻井液添加剂对形成天然气水合物的影响

针对深水钻井中水基钻井液易形成天然气水合物从而导致钻井作业无法正常进行的问题,利用自行设计研制的气体水合物反应装置,模拟深水钻井温度压力条件,对水基钻井液添加剂进行了天然气水合物形成的实验研究。分析了各实验体系形成水合物的过冷度。以过冷度为评价指标,评价了各种钻井液添加剂在深水钻井水合物形成过程中的作用。结果表明,在钻井液使用的加量范围内,阳离子聚丙烯酰胺CPAM、两性离子聚合物FA367等对天然气水合物的形成有抑制作用,且随着加量的增加抑制作用增强;磺甲基丹宁SMT、木质素磺酸盐FCLS对天然气水合物的形成有微弱的促进作用,但影响不大。聚合物添加剂的离子类型对天然气水合物的形成影响不大。     

天然气水合物形成的检测

研制的静态水合物试验装置采用可视观察的方法，可以快速确定天然气水合物的形成条件。动态天然气水合物试验装置在利用直接观测来判断水合物形成点的同时，通过监测装置转轮的扭距、试验介质的温度、压力、流速变化，综合判断天然气水合物的形成，此装置可以很好地模拟现场实际的天然气管输工况，实验结果与理论值及实际值差别较小。     

南海神狐海域天然气水合物开采数值模拟

实地钻探结果表明我国南海北部神狐海域存在大量天然气水合物,其作为未来我国潜在的可开发能源的调查和资源评价工作正在展开.利用国际上先进的多相多组分沉积物渗流模拟计算软件TOUGH+HYDRATE,以2007年5月国土资源部广州地质调查局在南海北部神狐海域SH2,SH3和SH7站位的钻探、测井数据为基础,建立实际水合物藏分层地质模型,利用不同的开采井设计方式进行单井降压和降压+注热开采模拟.结果表明,开采过程中水合物分解区域主要集中在开采井周边区域、水合物层与含水层界面处以及水合物层顶部靠近上盖层的区域.由于水合物分解吸热,水合物层的温度降低,使得热量从上盖层向水合物层传递,形成地温梯度的逆转,促进水合物层顶部逐渐产生分解界面.降压开采进行到后期开采井周围会形成渗透率很低的"二次水合物",影响开采的进行,所以利用降压+注热开采方法消除"二次水合物",使开采过程顺利进行.     

天然气水合物降压分解微观实验设计*

为了解决天然气水合物降压分解过程中孔隙尺度精细描述的难题,开展了天然气水合物微观可视模型实验设计。实验装置设计从具备可视功能、实时监测功能、数据处理功能和临界状态判断功能入手,开展了设备初始化调试、生成与分解模拟和产气效率分析等共3个层次实验内容。实验结果表明,学生不但能够定性描述水合物微观孔隙水合物生成与分解过程,而且实现了定量计算不同时刻水合物产气效率,这为学生对水合物微观生成与降压分解规律的理解奠定了基础。实验加深了学生对海洋油气工程专业知识的理解,提升了学生解决复杂工程问题的实践能力。     

Use of Electrical Resistance to Detect the Formation and Decomposition of Methane Hydrate

The changes of electrical resistance(R)were studied experimentally in the process of CH_4 hydrate formation and decomposition,using temperature and pressure as the auxiliary detecting methods simultaneously.The experiment results show that R increases with hydrate formation and decreases with hydrate decompositon.R is more sensitive to hydrate formation and decompositon than temperature or pressure,which indicates that the detection of R will be an effective means for detecting natural gas hydrate(NGH)quantitatively.     

Hydrate capture CO2 from shifted synthesis gas,flue gas and sour natural gas or biogas

CO₂ capture by hydrate formation is a novel gas separation technology, by which CO₂ is selectively engaged in the cages of hydrate and is separated with other gases, based on the differences of phase equilibrium for CO₂ and other gases. However, rigorous temperature and pressure, high energy cost and industrialized hydration separator dragged the development of the hydrate based CO₂ capture. In this paper, the key problems in CO₂ capture from the different sources such as shifted synthesis gas, flue gas and sour natural gas or biogas were analyzed. For shifted synthesis gas and flue gas, its high energy consumption is the barrier, and for the sour natural gas or biogas (CO₂/CH₄ system), the bottleneck is how to enhance the selectivity of CO₂ hydration. For these gases, scale-up is the main difficulty. Also, this paper explored the possibility of separating different gases by selective hydrate formation and reviewed the progress of CO₂ separation from shifted synthesis gas, flue gas and sour natural gas or biogas.     

Tuning methane content in gas hydrates via thermodynamic modeling and molecular dynamics simulation

Storage and transportation of natural gas as gas hydrate (“gas-to-solids technology”) is a promising alternative to the established liquefied natural gas (LNG) or compressed natural gas (CNG) technologies. Gas hydrates offer a relatively high gas storage capacity and mild temperature and pressure conditions for formation. Simulations based on the van der Waals–Platteeuw model and molecular dynamics (MD) are employed in this study to relate the methane gas content/occupancy in different hydrate systems with the hydrate stability conditions including temperature, pressure, and secondary clathrate stabilizing guests. Methane is chosen as a model system for natural gas. It was found that the addition of about 1% propane suffices to increase the structure II (sII) methane hydrate stability without excessively compromising methane storage capacity in hydrate. When tetrahydrofuran (THF) is used as the stabilizing agent in sII hydrate at concentration between 1% and 3%, a reasonably high methane content in hydrate can be maintained (∼85–100, v/v) without dealing with pressures more than 5 MPa and close to room temperature.     

Interfacial mechanisms governing cyclopentane clathrate hydrate adhesion/cohesion

The present work uses a micromechanical force apparatus to directly measure cyclopentane clathrate hydrate cohesive force and hydrate-steel adhesive force, as a function of contact time, contact force and temperature. We present a hydrate interparticle force model, which includes capillary and sintering contributions and is based on fundamental interparticle force theories. In this process, we estimate the cyclopentane hydrate tensile strength to be approximately 0.91 MPa. This hydrate interparticle force model also predicts the effect of temperature on hydrate particle cohesion force. Finally, we present the first direct measurements of hydrate cohesive force in the gas phase to be 9.1 ± 2.1 mN/m at approximately 3 °C (as opposed to 4.3 ± 0.4 mN/m in liquid cyclopentane).     

Towards a fundamental understanding of natural gas hydrates

Gas clathrate hydrates were first identified in 1810 by Sir Humphrey Davy. However, it is believed that other scientists, including Priestley, may have observed their existence before this date. They are solid crystalline inclusion compounds consisting of polyhedral water cavities which enclathrate small gas molecules. Natural gas hydrates are important industrially because the occurrence of these solids in subsea gas pipelines presents high economic loss and ecological risks, as well as potential safety hazards to exploration and transmission personnel. On the other hand, they also have technological importance in separation processes, fuel transportation and storage. They are also a potential fuel resource because natural deposits of predominantly methane hydrate are found in permafrost and continental margins. To progress with understanding and tackling some of the technological challenges relating to natural gas hydrate formation, inhibition and decomposition one needs to develop a fundamental understanding of the molecular mechanisms involved in these processes. This fundamental understanding is also important to the broader field of inclusion chemistry. The present article focuses on the application of a range of physico-chemical techniques and approaches for gaining a fundamental understanding of natural gas hydrate formation, decomposition and inhibition. This article is complementary to other reviews in this field, which have focused more on the applied, engineering and technological aspects of clathrate hydrates.     

Experimental study on flow characteristics of tetrahydrofuran hydrate slurry in pipelines

Tetrahydrofuran (THF) was selected as the substitute to study the flow behaviors and the mechanism of the hydrates blockage in pipelines. The slurrylike hydrates and slushlike hydrates are observed with the formation of hydrates in pipeline. There is a critical hydrate volume concentration of 50.6% for THF slurries and pipeline will be free of hydrate blockage while the hydrate volume concentration is lower than the critical volume concentration; otherwise, pipeline will be easy to be blocked. Fully turbulent flow occurs and friction factors tend to be constant when the velocity reaches 1.5 m/s. And then, constant values of friction factors that depend on the volume concentrations in the slurry were regressed to estimate the pressure drops of THF hydrate slurry at large mean velocity. Finally, a safe region, defined according to the critical hydrate volume concentration, was proposed for THF hydrate slurry, which may provide some insight for further studying the natural gas hydrate slurries and judge whether the pipeline can be run safely or not.     

Energy-efficient methods for production methane from natural gas hydrates

Gas hydrates now are expected to be one of the most important future unconventional energy resources. In this paper, researches on gas hydrate exploitation in laboratory and field were reviewed and discussed from the aspects of energy efficiency. Different exploiting methods and different types of hydrate reservoir were selected to study their effects on energy efficiencies. Both laboratory studies and field tests have shown that the improved technologies can help to increase efficiency for gas hydrate exploitation. And it also showed the trend that gas hydrate exploitation started to change from permafrost to marine. Energy efficiency ratio(EER) and energy return on energy invested(EROI) were introduced as an indicator of efficiency for natural gas hydrate exploitation. An energy-efficient hydrate production process, called "Hydrate Chain Energy System(HCES)", including treatment of flue gas, replacement of CH4 with CO2, separation of CO2 from CH4, and storage and transportation of CH4 in hydrate form, was proposed for future natural gas hydrate exploitation.In the meanwhile, some problems, such as mechanism of CO2 replacement, mechanism of CO2 separation,CH4 storage and transportation are also needed to be solved for increasing the energy efficiency of gas hydrate exploitation.