输气管线中天然气水合物的防治

天然气水合物是由天然气和水在高压低温条件下形成的类冰结晶状化合物。天然气储运过程中,天然气水合物常常造成管道、阀门和设备等的堵塞,降低了管道的输送能力。因此水合物的防治工作对于石油天然气工业日趋重要。针对水合物的防治可采取物理和化学措施,例如脱水法和添加抑制剂等。抑制剂主要包括热力学抑制剂、动力学抑制剂、防聚剂三种类型,开发环保并且低廉的动力学抑制剂和防聚剂是防治水合物的发展方向。     

天然气水合物导热性能研究现状

天然气水合物导热系数的研究对于模拟自然界天然气水合物的成藏和天然气水合物勘探、开采具有重要意义。本文介绍了获取天然气水合物导热系数的实验测试和模拟计算方法,分析了气体水合物导热特性、导热机理以及水合物复合体系导热。总结了水合物导热规律,即外界温压条件和晶穴占有率对水合物的导热产生影响,且水合物的导热具有相似的温度压力依赖关系,并呈玻璃体的导热特性。水合物玻璃体导热特性由水合物笼型结构决定,而客体分子的存在强化了水合物导热的玻璃体属性。指出非稳态下天然气水合物导热性能变化研究对分析天然气水合物在常压下的稳定性、确定甲烷水合物等最佳储存温度、从导热角度探讨自保护效应机理等具有重要意义。     

一种新型天然气储存技术及其应用前景

天然气水合物（NGH）是在低温高压的条件下由水和天然气形成的笼形结晶化合物。天然气水合物储气技术是一种新型的天然气储气技术，具有能量密度高、安全可靠、费用低等优点。文章介绍了天然气水合物的制备、储气性能以及应用前景。     

世界天然气水合物资源勘探开发现状与展望

综述了世界天然气水合物资源状况（储量约为2×10^16m^3）、分布以及主要国家的勘探开发动向。介绍了天然气水合物的勘探方法（地球物理勘探法、地球化学勘探法、标型矿物法、自生沉积矿物学法等）,以及天然气水合物的开发技术（加热法、降压法、添加化学剂法、驱替法等）。列举了世界天然气水合物开发项目的一些实例。对天然气水合物勘探开发前景进行了展望。     

金属纤维悬浮液中天然气水合物生成特性实验研究

水合物缓慢的生成速率已经成为水合物储运天然气技术应用的一大障碍。基于静态强化水合物生成技术,以含悬浮金属纤维的表面活性剂溶液作为水合储气介质,研究4.0～7.0 MPa下天然气水合物在悬浮溶液中的生成动力学特性。研究结果表明,金属纤维优良的导热性能够促进水合物快速生成,同时纤维的粗糙表面可促进水合物成核,水合物在金属纤维悬浮体系中的储气量与储气速率均明显高于表面活性剂溶液中的水合特性。在实验压力下,悬浮体系中水合物成核诱导时间明显降低,同时储气量可以达到87.3～129.6 m³·m^-3,比表面活性剂溶液中的增加了5.0%～23.4%;储气速率达到4.4～25.1 m³·（m³·min）^-1,比表面活性剂溶液中的提高了1.1%～39.8%。研究结果可为水合物储气技术在天然气储运方面的应用提供技术参考。     

瞬态热线法测量煤层气水合物导热系数的实验研究

煤层气(瓦斯)的储存和运输是实现煤层气能源利用的重要前提,水合物法是将来煤层气等气体固化储运的主要技术之一。煤层气水合固化储运过程受热量传递的控制,而开展瓦斯水合物的热量传递机理研究,其导热系数是必须要知道的热物性参数。基于瞬态热线法原理,建立了一套测试设备对瓦斯水合物的导热系数进行了实验研究,获得该瓦斯水合物样品导热系数及其和温度的关系。从瓦斯水合物的热物性因素方面支持了以NGH(水合物储运)形式对瓦斯进行水合固化储运的可行性。     

天然气水合物开采的方法及对环境的影响

介绍了天然气水合物形成机理。介绍了热力开采法、降压法、分解促进剂注人法、CO2置换法等目前世界上主要的开采方法原理、工艺及适用范围等。分析了开发天然气水合物对自然环境的影响,对我国进行天然气水合物开发提出了建议。     

BSR与CSEM识别天然气水合物的优缺点对比

天然气水合物是一种分布广泛的新型清洁能源,是目前能源勘探界的研究热点之一。提升天然气水合物勘探技术以探测天然气水合物分布和进行资源量估算,对我国天然气水合物的开采和利用至关重要。本文对比总结了似海底反射（BSR）和海洋可控源电磁法（CSEM）识别天然气水合物的优势与局限性。结果表明,BSR是目前识别海洋天然气水合物的一种常用且重要的方法,但BSR与天然气水合物的存在并非一一对应,难以准确估算天然气水合物饱和度和资源量。海洋CSEM能相对准确地识别天然气水合物,并可通过获取储层电阻率估算天然气水合物饱和度和储量。两者的结合将有效提高天然气水合物的钻探成功率、降低勘探风险和节约勘探成本。     

天然气水合物开采方法的应用——以Ignik Sikumi天然气水合物现场试验工程为例

天然气水合物已成为世界各国关注的焦点,对天然气水合物开采方法的研究、实践和应用是目前的重点之一.天然气水合物的开采方法主要包括注热法、降压法、注化学试剂法、气体置换法等4种以及这些方法的联用,其中注热法因能耗较大和生产层必须具有良好的孔隙度而使其成本显著提高;降压法无需消耗大量能源,因而被认为是最可行且最具经济价值的天然气水合物生产方法,这一方法可能最适合含水合物盖层以下圈闭有大量气体的矿床;注化学试剂法不是分解天然气水合物的主要方法,不适合长期或大规模使用,且成本较高;气体置换法是通过客气分子的注入来置换天然气水合物中的甲烷,使甲烷释放到孔隙流体中,在被气相包裹的水合物中,气体置换有效率可超过60％,该方法的主要制约因素是水合物储层的低渗透性.2012年5月,在美国阿拉斯加北坡完成了首个用于调查研究天然气水合物藏中CO2-CH4置换潜力的现场试验工程——Ignik Sikumi天然气水合物现场试验,成功注入约6000m3二氧化碳和氮气混合气体,累计生产气体近3× 104m3,未对储层造成压裂破坏.该试验工程为水合物领域的科学研究提供了大量的数据和新的认识,美国能源部也因此宣布了新的研究举措.     

元坝气田高含硫气藏水合物防治技术研究

在正常生产过程中一旦形成天然气水合物,会使井筒及流程管线内形成水合物冰堵现象,造成流程堵塞、超压,严重影响安全生产,形成安全隐患。此外,随着越来越多的高含硫气藏投入开发,硫化氢对于水合物形成的影响也越来越受到关注。影响天然气水合物生成的因素有内因与外因,包括天然气组分、温度、压力、离子浓度、搅拌速率、生产系统情况等方面,硫化氢对水合物形成的影响主要体现在硫化氢体积分数对水合物形成温度的影响和硫化氢对天然气含水饱和度的影响两方面。针对元坝高含硫气田的水合物形成提出相应的防治措施,包括井筒水合物和地面水合物的防治措施。目前井筒水合物防治措施主要有加热法、化学抑制法、隔热保温法、油管内涂厌水层法、产量控制法、井下节流法等;地面水合物的防治措施主要有加热法、化学剂法和天然气脱水法。     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.     

天然气水合物的研究及利用

介绍了水合物的形成和抑制机理，以及多种预测水合物形成条件的模型；分析了用水合物储存和运输天然气面临的问题，各种水合物促进剂的作用机理以及对水合物生成速度、储气密度的影响；叙述了开采、利用天然气水合物资源的研究进展和一种将水合物转化成液体燃料的方法。     

多孔介质中甲烷水合物的生成特性研究进展

天然气水合物是一种清洁高效的能源,常常在自然界中的海底沉积物多孔介质孔隙中生成,同时水合物在工业上还能与多孔介质材料一起作为储存及分离气体的一种方式,因此开采利用水合物以及发挥水合物工业技术的前提都跟多孔介质有莫大的关系,对多孔介质中天然气水合物生成特性的研究进行总结与分析具有非常重要的意义。本文总结分析了国内外关于不同类型多孔介质中甲烷水合物的生成过程及特性的研究文献,将多孔介质根据其孔径大小进行划分。结果显示,在微孔介质中,甲烷水合物的生成侧重于气体的存储及运输方面;在介孔介质中,甲烷水合物的生成动力学受孔径影响较大;在大孔的沉积物中,甲烷水合物的生成及分布的机理性研究仍比较缺乏。因此,需要进一步的研究来丰富甲烷水合物在多孔介质中的生成动力学理论,本文将在文献调研的基础上为今后的研究方向提出一些展望和思路。     

An experimental investigation into the effects of zeolites on the formation of methane hydrates

Methane hydrate is an ice‐like nonstoichiometric compound that forms when methane reacts with water at high pressures and low temperatures. It has a lot of practical applications such as separation processes, natural gas storage transportation, and carbon dioxide sequestration. Especially, the industrial use of hydrates requires large amounts of gas to be formed quickly into hydrates. Porous media significantly influence the rate of hydrate formation by reducing the chemical barrier, where zeolites are microporous minerals. This paper deals with natural and synthetic (5A and 13A) zeolites for hydrate formation and gas storage capacity. The results show that methane hydrates are formed much faster in the three zeolite solutions tested compared with their formation in distilled water at low subcooling temperatures (<7 K). It was also observed that the gas consumption was the greatest in the 0.01 wt.% zeolite 13X solution of distilled water. Its gas consumption was 5.1 times that of distilled water at 0.5 K subcooling. Zeolite 13X demonstrated its effectiveness in enhancing and expediting methane hydrate formation. Copyright © 2014 John Wiley & Sons, Ltd.     

Adsorption technology for the storage of natural gas and biomethane from biogas

As natural gas, biogas has been used for nobler purposes in recent years, such as the use of purified biogas (biomethane) in the transport sector. Currently, natural gas storage for use in transportation is accomplished primarily through compressed natural gas (CNG) technologies and liquefied natural gas (LNG), which require large amounts of energy. In recent years, the storage technology of absorbed natural gas (ANG) on porous materials has been studied, fundamentally highlighted by reduced energy use and increased safety in the transport of gaseous fuel. In this sense, the present study aimed to gather information about the main adsorbent materials which are being studied and the conditions normally employed in surveys that use ANG technology, as well as pointing out the main challenges for the storage of biogas in the adsorbed form at low pressures and room temperature in an attempt to meet the target of 180 V/V established by Department of Energy. Researchers reported high storage capacities in moderate conditions of temperature and pressure; however, the biggest challenge of the research involving methane adsorbed is also achieving high rates of desorption with the lowest possible energy expenditure. Copyright © 2016 John Wiley & Sons, Ltd.     

Mechanical experiments and constitutive model of natural gas hydrate reservoirs

Natural gas hydrate is a new type of green energy resources and has great development prospects, and it has attracted worldwide attentions. The exploitation of natural gas hydrate may result in a series of geological disasters. Therefore, the constitutive model of natural gas hydrate bearing sediments needs to be established to reveal deformation laws of the reservoir sediments and accurately evaluate mechanical properties of hydrate reservoirs. This is the basic guarantees for the effective exploitation of natural gas hydrate resources. The triaxial compressive tests were conducted on samples of natural gas hydrate sediment. Furthermore, the Duncan-Chang hyperbolic model was modified by considering the influences of hydrate saturation based on the test results to obtain the constitutive model according with the deformation characteristics of natural gas hydrate reservoirs. The results show that the stress-strain curves of natural gas hydrate reservoirs show unobvious compaction stage and peak strength, short elastic stage, long yield stage, and significant strain hardening characteristics. After applying loads on natural gas hydrate bearing sediments, the internal solid particles were dislocated and slid. When the loads were small, the sediments demonstrated elastic deformation. With the increase of loads, plastic flows appeared in the interior, and the hydrate crystals were re-orientated, thus the sediments showing plastic deformation. Initial tangent elastic modulus increased with the effective confining pressures, which had little correlations with hydrate saturation. Furthermore, the damage ratio increases with the increase of effective confining pressures, while slightly decreases with the increase of natural gas hydrate saturation. The predicted results of stress-strain curves of sediments with different hydrate saturations well coincide with the results of triaxial compressive tests, indicting the feasibility and rationality of this model.     

“CH4-CO2”置换法开采天然气水合物

天然气水合物作为一种储量巨大的清洁能源,其开采价值已引起越来越多的关注。当前天然气水合物开采技术仍不足以商业化应用,还需进一步的实验研究进行理论支撑。二氧化碳置换开采天然气水合物被认为是能同时实现天然气水合物开采与二氧化碳减排、封存的双赢技术,近年来得到了较广泛的研究。置换过程中,混合天然气水合物的热力学和结构性质是预测含水合物沉积物中的热流和水合物解离所需的热量以及评估水合物储层的CO₂储存能力的关键因素。本综述在调研国内外天然气水合物开采技术研究现状的基础上,围绕CO₂置换开采天然气水合物的热力学特性、微观机理与置换效率等,总结了各研究取得的成果,针对置换研究中存在的问题进行了分析,认为当前置换法开采天然气水合物最关键难点在于提高置换效率,而解决该问题的根本在于从热力学和动力学角度弄清楚置换反应的微观机理及控制性因素,明确置换机理,从而在未来的研究有的放矢。