Predicting the conditions for gas hydrate formation

Gas hydrate is a crystalline mixture obtained from gas molecules trapped in the cavity of hydrogen bonding water. To date, an essential step in the development of natural gas industry has been the acquisition of knowledge in the operation and handling of gas under high pressure without hydrate formation. Since there are several ways to predict hydrate formation, this study investigates predicting hydrate formation using the Katz method. In addition, several new models for accurate estimation of gas hydrate formation conditions will be provided. These models are based on artificial neural network (ANN) requirements. To create the model, predictive experimental data published in books and journals, as well as data extracted from Katz graph (Katz chart), estimate the formation conditions of gas hydrate. We validate the model created with the use of various statistical parameters such as mean squared error (MSE) and R²-value. The result of these parameters in models created to predict the formation of hydrates accurately and efficiently is evaluated. In this study, our goals are to use an artificial intelligence neural network to predict the formation of gas hydrates.     

An intelligent optimization–based prediction model for natural gas hydrate formation in a deepwater pipeline

Temperature, pressure, and composition of gas mixtures in deepwater pipelines promote rapid formation of gas hydrates. To avert this dilemma, it is more significant to find out the temperature and pressure limits in gas hydrates formation of the deepwater pipeline. The objective of this research is to develop an optimization method that finds the optimal temperature and pressure profile for natural gas hydrate formation conditions and an error calculation method to find the realistic approach of the hydrate formation prediction model. A newly developed correlation model is computing the hydrate formation pressure and temperature for a single component of methane (CH₄) gas. The proposed developed prediction model is based on the 2 and 15 constant coefficients and holds a wide range of temperature and pressure data about 2.64 to 46°C and 0.051 to 400 MPa for pure water and methane, respectively. The reducing error discrepancies are 1.2871, 0.35012, and 1.9052, which is assessed by GA, PSO, and GWO algorithms, respectively. The results show the newly developed optimization algorithms are in admirable compliance with the experimental data and standards of empirical models. These correlations are providing the capability to predict gas hydrate forming conditions for a wide range of hydrate formation data.     

Model of transient CO2 gas hydrate particle size distribution at its equilibrium condition

Abstract

It is important to comprehend the relationship between temperature and pressure at which different sizes of hydrates with a particular distribution. When hydrate particles are formed at unsteady state condition, the moment and the spreadness of the distribution of the formation of the hydrate particles is changed with time. The change of distribution of hydrate particle is one of the important parameter for the secondary nucleation rate of gas hydrate. In this study, a model is developed and proposed to predict the particle size distribution of carbon dioxide gas hydrate at its equilibrium condition. The distribution model may be useful for further understanding of the nucleation mechanism and its rate of gas hydrate formation.     

Research on hydrate formation and prevention during deepwater gas wells cleanup stage

Abstract

Wellbore cleanup is an important part of deepwater gas wells completion testing and also a critical stage for hydrate formation. For evaluating hydrate risk and proposing specific hydrate prevention-control measures, based on multiphase flow theory, combined hydrates formation-deposition characteristics, the flow risks under different discharge stages are evaluated. It is concluded that hydrate formation in annular flow pattern needs to be focused on importantly. Meanwhile, the research results were verified with the cases of deepwater gas wells in the South China Sea. Finally, the hydrate risk period and critical discharging institution were determined for deepwater gas wells. Optimizing the inhibitor injection time and the amount of the inhibitor injection, combining the discharge pressure differences reasonably can play an economical and effective role in preventing and controlling hydrate risk during deepwater gas well cleanup stage.     

Modelling of methane hydrate formation pressure in the presence of different inhibitors

Formation of gas hydrates is one of the problems in the production, processing, and transportation of natural gas. Hence, an understanding of conditions where hydrates form is necessary to overcome hydrate-related issues. The aim of this study was to develop an effective relation between the methane hydrate formation pressure based on the temperature, weight fraction of inhibitor, and molecular weight of inhibitor using the least square support vector machine. This computational model indicates the great ability of predictions for determining hydrate pressure in the presence of different inhibitors such as the methanol, ethylene glycol, diethylene glycol, and triethylene glycol. The values of R-squared (R²) and mean squared error obtained for this model are 0.9925 and 0.2325, respectively. This developed predictive tool can be applied as an accurate estimation of methane hydrate formation pressure.     

我国台西南附近构造沉降与沉积作用对气水合物成藏的可能控制

南中国海东北部大陆斜坡带上的海相沉积有适当的沉积厚度,处于适宜形成气水合物的温―压域内,有一定的甲烷生成潜力。从台西南盆地的地震反射记录中,可以观察到气水合物存在的证据――似海底反射(BSR),暗示了气水合物的广泛分布。台西南盆地的构造沉积格架与甲烷的生成和大量气水合物沉积可能存在直接联系;各种快速堆积的沉积体系(如滑塌块体、等深流沉积、浊积扇及三角洲)前缘,是天然气水合物富集的有利沉积相带,其中等深流沉积和滑塌块体推测为最有利气水合物聚集的沉积体。     

基于支持向量机结合遗传算法的天然气水合物相平衡研究

天然气水合物(以下简称水合物)具有高储气率和高可靠性等优点,在天然气储存及运输方面具有广泛的应用前景,同时水合物的存在也会给输气管道带来堵塞等严重影响,因此对水合物的生成研究具有重要意义。为此,对Ⅰ型水合物在无添加剂条件下的静态生成规律进行了研究。首先基于水合物动力学实验装置进行一系列实验,然后利用支持向量机(SVM)结合遗传算法(GA)建立了水合物生成预测模型(SVM+GA)。据此将实验中得到的温度和压力数据进行预测和优化处理,并对上述数据进行非线性拟合,得出了相平衡曲线及其方程,计算得出了常温下生成水合物的相平衡压力为33.5 MPa,常压下生成水合物的相平衡温度为237.1 K。将分别由SVM+GA模型、Chen-Guo模型和vd W-P热力学模型所得到的数据与经典的实验数据进行了对比,其平均相对误差分别为2.678%、1.447%和3.249%。结论认为:SVM+GA模型具有较高的计算准确度,比Chen-Guo模型和vd W-P热力学模型更为简便,可为水合物开发研究提供更多的数据。     

高温高压气井测试期间水合物防治技术研究

从测试井筒温度压力场的分布规律研究入手,预测分析高温高压井测试过程中水合物生成可能性,建立了高温高压测试期间井筒温度和压力场理论计算模型,通过室内模拟实验建立了天然气水合物生成条件的预测模型,结合高温高压井测试期间现场情况,提出了水合物防治的具体措施,进一步降低了测试作业施工过程中事故和风险。     

A new empirical correlation for prediction of gas hydrate dissociation equilibrium

Abstract

To prevent the plug of hydrate it is important to study the relationship between temperature and pressure at which hydrate form and dissociate. An empirical correlation was developed to predict the equilibrium condition to form the gas hydrate with and without presence of inhibitors. Overall 600 data points of equilibrium, to form gas hydrate have used to obtain the empirical correlation. The overall average absolute deviations are found to have good agreement with the experimental data. The present study may be helpful for further understanding the correlation of gas hydrate formation equilibrium condition.     

Computation of equilibrium hydrate formation temperature for CO2 and hydrocarbon gases containing CO2 in the presence of an alcohol, electrolytes and their mixtures

This work presents the applicability of a unified model to predict the CO₂-rich gas and pure CO₂ hydrate formation conditions in aqueous solutions containing glycerol, methanol, ethylene glycol, electrolytes and their mixtures. A water activity model is introduced that combines the effect of the soluble gases, an alcohol and electrolytes. Then this model is used together with the model of Holder et al. [Holder, G.D., Corbin, G., Papadopoulos, K.D., 1980. Thermodynamic and molecular properties of gas hydrates from mixtures containing methane, argon and krypton. Ind. Eng. Chem. Fundam. 19 (3) 282] to predict CO₂-rich gas and CO₂ hydrate formation conditions. The predictions are in excellent agreement with experimental data.     

The Simulation of Gas Production from Hydrates by Depressurization at a Constant Pressure

Abstract

A general-purpose simulator for gas production from hydrates is developed, which considers kinetics of dissociation, heat, and multiphase fluid flow. Production behavior of the Class I hydrate reservoir by depressurization technique is studied. The results suggest gas production rate at the well is higher than gas release rate in the reservoir and most water released is left in pores. With continuous dissociation of hydrate, average hydrate saturation, reservoir temperature, and pressure decrease continuously. In addition, the closer to gas layer, the faster the hydrate dissociation. Results of gas production simulations can provide theoretical basis for the development of hydrates in the future.     

海洋天然气水合物地层钻井液优化实验研究

海洋天然气水合物（以下简称水合物）地层钻井过程中，钻井液侵入地层有可能造成水合物分解，进而引发井壁失稳等问题。为了破解上述难题，实验研究了甲烷水合物在不同分解方式下的分解规律，引入Peng-Robinson方程计算实验过程中甲烷气体摩尔数的变化，优化了钻井液抑制水合物分解评价实验方法，并利用该方法实验分析了动力学抑制剂DY-1和改性卵磷脂对水合物分解特性的影响规律，进一步优化出适用于水合物地层使用的水基钻井液。研究结果表明：①注冷溶液不卸压的方式是钻井液抑制水合物分解最佳的评价实验方法；②水合物动力学抑制剂DY-1和改性卵磷脂均可通过吸附在水合物表面阻缓传热传质来延缓水合物分解，可作为钻井液水合物分解抑制剂；③优化出的钻井液体系具有良好的低温流变性和抑制水合物生成及分解性能，同时具有良好的页岩抑制性和润滑性等，可以满足海洋水合物地层钻井液技术的基本要求。结论认为，该研究成果可以为我国水合物开发提供钻井液技术支撑。     

普光气田采气井口水合物预测与防止技术

普光气田天然气为高含硫过成熟干气，在采气过程中容易形成水合物，而采气井口属于水合物形成的高发部位，一旦形成将严重影响正常生产。为此，筛选适合普光气田的水合物预测模型，进行了水合物形成预测；同时基于渗流理论和产能方程，模拟气田衰竭式开发过程，利用wellflo软件计算了普光2井在不同地层压力、不同产气量下井口的压力和温度分布，并对采气井口水合物的形成进行了预测与防止技术研究。结果表明：当地层压力一定时，随着产气量降低，采气井口更易形成水合物；当产气量大于10×10⁴m³/d时，井筒及井口不会形成水合物。在此基础上，提出了冬季或温度较低时应对井口装置采取隔热保温或加热措施，低产时应考虑在井口注化学剂的预防措施。     

甲烷水合物在煤层中存在的可能性

已有实验证明：在一定的温度下，只要压力合适，有甲烷气源和水，就能合成甲烷水合物，而且多孔介质的存在将有助于水合物的形成。煤是一种多孔介质，在其形成过程中生成了大量的甲烷，并含有大量的水份。受构造应力和地应力的影响，煤层中存在着褶皱、断层等，结构复杂，因而在煤层中存在高应力区，而这种高应力区为甲烷水合物的存在创造了条件，同时，在一些煤与瓦斯突出中，吨煤瓦斯突出量高出吨煤瓦斯含量很多，以致无法解释，更为煤层中的局部地点存在甲烷水合物提供了佐证。因此，推断煤层中可能存在零散分布的甲烷水合物。     

预防气体水合物堵塞的深水油气井测试安全阀下入位置研究

深水油气井测试过程中,容易发生气体水合物堵塞井下安全阀的问题,为避免出现该问题,研究了安全阀合理下入位置的确定方法。利用气体水合物相平衡微观试验装置,在室内模拟了地层水矿化度下多组分气体水合物在水中的相变过程,得到了温度和压力对气体水合物相平衡的影响规律;分析了气体组分、水深、地温梯度和井口压力对生成气体水合物的影响,预测了气体水合物的生成区域,从安全和成本2方面考虑给出了安全阀最小下入深度的确定方法。研究发现,气体组分、水深、地温梯度、井口压力均会影响安全阀的下入位置,产出气中乙烷、丙烷和丁烷含量增加更易生成气体水合物;同时,水深越深,地温梯度越小,井口压力越大,生成气体水合物的区域越大,安全阀需要下入到更深的位置。研究认为,上述研究成果可为深水油气井测试中安全阀下入位置的确定提供参考。      

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随着高压气井的不断勘探与开发，由于受气体的焦耳－汤姆逊效应的影响，高压条件下天然气水合物形成条件的预测愈加重要。针对高压气井测试与生产过程中的压力高、流速高、天然气及地层水成分复杂等特点，应用热力学理论，结合部分室内实验，研究水合物的形成条件和预测方法，建立了计算模型和预测软件，以判断和预防高压测试系统中水合物的形成。还介绍了在水合物生成条件计算方法的基础上，利用实测数据，对计算结果进行的验证。结果表明计算误差较小,可用于高于100MPa压力条件下的计算。     

深水气井测试管柱内天然气水合物堵塞特征与防治新方法

目前对于深水气井测试过程中井筒管柱内天然气水合物(以下简称水合物)堵塞的形成机制尚不清楚,因而存在着过度使用水合物抑制剂以及抑制剂利用效率较低等问题。为此,针对多相流,在水合物生成动力学、水合物颗粒运移沉积动力学等方面开展了研究:构建形成水合物堵塞的定量预测模型,预测水合物在管柱内何时何处形成堵塞并评估堵塞严重程度,确定易发生堵塞的高风险区。进而提出了基于拓展安全作业时间窗口的水合物堵塞防治新方法——依据安全作业时间窗口优选抑制剂浓度、优化抑制剂注入速率。研究结果表明:(1)井筒内所生成的水合物在管柱内壁上沉积附着,形成不断增厚的水合物层,造成管径变小,液膜处生成的水合物在管壁上沉积是造成管柱堵塞的主要原因;(2)随着水深增大或产气量降低,不发生水合物堵塞的安全作业时间窗口变窄,形成堵塞所需时间变短;(3)注入水合物抑制剂可以延缓堵塞的发生,拓宽安全作业时间窗口;(4)水合物防治新方法可显著降低所需水合物抑制剂用量和注入速率(在算例条件下可降低50%)。结论认为,新方法有效克服了传统方法过度使用水合物抑制剂的不足,可为深水气井测试中水合物的防治提供指导。     

天然气水合物生成的影响因素及敏感性分析

天然气水合物是由某些气体或它们的混合物与水在一定温度、压力条件下生成的一种冰状笼型化合物。进行水合物生成条件的敏感性研究对预防天然气水合物的生成有着重要意义。分析了温度、压力两个主导因素的影响,提出了临界温度的概念;验证了盐类对水合物生成的抑制作用;剖析了天然气各组分对水合物生成的敏感程度。得出:水合物生成温度随着压力的增加而升高,但是存在一个临界温度,当环境温度达到该值时,压力对水合物生成的影响很小;甲烷虽然是生成水合物的主要组分,但当其含量趋近100%时,却不易形成水合物;乙烷不是敏感组分;丙烷对水合物生成的影响较乙烷大;异丁烷这类重烃组分,由于其分子大小和Ⅱ型结构中的大洞穴尺寸相匹配,所以对Ⅱ型结构的稳定能力远大于其它分子,当其含量较小时,就易生成Ⅱ型结构水合物;CO2和HS这类酸性气体,易溶水从而能促进水合物的生成。     

“自保护”态CO2水合物分解动力及影响因素

水合物"自保护"效应对利用水合物法进行天然气运输以及二氧化碳运输、封存具有重要应用价值,但目前此现象的成因尚未被彻底阐释。采用恒压、降温的方法在不同温度条件下于超纯水、十二烷基硫酸钠(SDS)溶液中形成不同含气量的CO2水合物并迅速冻结,使其进入"自保护"状态。随后通过均匀升温法分解不同条件下"自保护"态的水合物,并测量气体释放速率及起始分解温度。将气体释放速率对累积释放气体量一次求导,以表征分解过程中水合物释放气体能力。结果发现,阐释水合物"自保护"效应成因的"冰壳"理论不能完全解释实验结果,"自保护"效应更倾向于由"过冷水"理论主控。结合有关学者在水合物分解时溶液中形成的微型(微米、纳米级)气泡方面的研究结果,提出:CO2水合物"自保护"效应更倾向于由"自保护"状态下水合物周围存在的过冷液态水,以及水合物初步分解时液态水内溶解的微型(微米、纳米级)气泡控制。     

多孔介质中天然气水合物生成的主要影响因素

目前有关天然气水合物(以下简称水合物)的研究主要集中在物理化学性质考察和开采(分解)方法探索方面。在进行后者的研究过程中,地层渗流过程的物理模拟至关重要,但目前借助于石油开采研究中广泛应用的填砂管等多孔介质对水合物进行动态过程的研究却鲜有报道。为此,利用河砂填砂管在岩心驱替装置上进行了甲烷水合物生成过程的物理模拟,考察了地层温度、甲烷压力及地层模型性质参数等对水合物生成过程的影响。结果表明:(1)利用冰融水作为地层模型的束缚水可显著提升甲烷水合物的生成速率;(2)多孔介质条件下过程驱动力(即实验压力或温度偏离水合物相平衡对应值的程度)对甲烷水合物的生成起着决定性作用;(3)当甲烷压力高于水合物相平衡压力1.4倍以上,或者实验温度低于相平衡温度3℃以下时,甲烷水合物生成诱导期几乎不随温压条件的变化而变化;(4)渗透率、含水饱和度、润湿性等参数对实验中甲烷水合物的生成率不构成明显影响。