水合物藏降压开采实验及数值模拟

建立了降压法开采水合物藏数学模型,考虑了气-水-水合物-冰相多相渗流、水合物相变及分解动力学过程、冰-水相变、热传导、对流过程、渗透率变化等对于水合物分解的影响。三维水合物藏模拟表明:在开采前期阶段,可采用降压法,但随着储层能量消耗,产气速度下降很快,需转变开采方式。分析了一些主要参数,如孔隙度、渗透率、饱和度、压力等对水合物开采的影响。     

热力法开采地层天然气水合物的热动力评价

本文在推导热力作用下水合物地层温度分布基础上,发展了评价热力法开采天然气水合物的热效率(用于水合物分解的热量与输入总的热量之比)和能量效率(即输出能量与输入能量之比)的模型.模型分析表明,水合物地层热物性参数以及水合物饱和度决定了热力法开采的能量效率.在注入蒸汽开采初始条件下,能量效率可以达到7.0.     

用分子动力学模拟甲烷水合物热激法分解

用分子动力学模拟方法研究甲烷水合物热激法分解，系统地研究注入340 K液态水的结构Ⅰ型甲烷水合物的分解机理.模拟显示水合物表层水分子与高温液态水分子接触获得热能，分子运动激烈，摆脱水分子间的氢键束缚，笼状结构被破坏.甲烷分子获得热能从笼中挣脱，向外体系扩散.热能通过分子碰撞从外层传递给内层水分子，水合物逐层分解.对比注入277K液态水体系模拟结果，得出热激法促进水合物分解. 关键词： 甲烷水合物 分子动力学模拟 热激法     

水流动强化天然气水合物降压分解研究

降压法被认为是最经济可行的天然气水合物开采方法,但开采后期驱动力不足、甚至产生水合物的二次生成,因此其应用受到限制。本文将降压法与水流动结合提升水合物分解驱动力,研究不同降压模式和水流动对天然气水合物分解特性的影响。发现当降压结合水流动时,压降为水合物分解提供初始驱动力,且压降越大水合物分解驱动力越大。同时水流动能够加快传热传质过程,为水合物分解提供额外的驱动力。在快速降压结合水流动模式中,较高背压下水流动为水合物分解提供主要的驱动力;在梯度降压结合水流动模式中,降压和水流动共同为水合物提供分解驱动力,对水合物分解的促进作用更加显著。     

海洋天然气水合物模拟实验的超声检测

本文主要描述自行开发的U-sonic超声检测仪对天然气水合物在合成和分解过程中声学参数(如声速、频率、幅度)的变化进行声学检测,找出声学参数与水合物形成和分解之间的变化规律,以达到判断和预测水合物形成和分解的目的。     

用分子动力学模拟甲烷水合物热激法结合化学试剂法分解

用分子动力学模拟方法研究甲烷水合物的热激法，化学试剂法，以及热激法结合化学试剂法分解，系统研究温度为277K和340K时添加液态水(WTR)和30wt％乙二醇(EG)溶液对水合物分解的影响.模拟显示WTR与水合物表面水分子形成氢键，破坏水合物原有的氢键平衡，造成笼状结构坍塌，水合物分解.EG分子中的羟基与水合物表面水分子形成氢键，从而破坏原有的稳定结构，造成水合物笼状结构被破坏，达到促进水合物分解，释放甲烷气体的效果.比较温度为277K和340K时添加WTR和30wt％EG溶液对水合物分解效果得出EG(340K)> WTR(340K)>EG(277K)>WTR(277K)，热激法结合化学试剂法能更好促进水合物分解.     

裂缝性应力敏感油藏流固耦合的数值模拟

以裂缝各向异性全张量渗透率动态耦合渗流模型为基础,建立三维三相裂缝各向异性特低渗透油藏流固耦合数学模型,并运用模块化显示耦合迭代求解建立流固耦合渗流数值模拟方法,编制耦合求解程序.研究表明:对于裂缝性油藏,随着油藏开采过程中压力的变化,岩石变形和储层介质的各向异性应变特性使开发过程中多组裂缝的变形程度不同,引起裂缝渗透率的非线性变化,进而使油藏裂缝渗透率张量主值发生旋转,改变液流方向、影响油藏开发效果.     

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。     

CH4水合物生长速率影响因素的分子动力学模拟

采用分子动力学模拟,研究了温度、压力和电解质溶液对CH4水合物生长速率的影响.通过分析势能、均方位移、氢键数量、径向分布函数和四体结构有序参数,表征了CH4水合物的生长动力学.模拟结果表明,降低温度和提高压力可以显著提高CH4水合物的生长速率.当压力恒为15MPa,温度高于290K时,势能升高,CH4水合物晶体发生分解;温度由290K降至260K时,势能降低,CH4水合物持续生长.当温度恒为275K,压力由3MPa增至50MPa时,CH4水合物生长速率提高12%.此外,电解质离子的存在抑制了水合物的生长,电解质溶液浓度由1.5wt%增加到3.5wt%时, CH4水合物生长速率降低25%.     

Numerical Investigation into the Gas Production from Hydrate Deposit under Various Thermal Stimulation Modes in a Multi-Well System in Qilian Mountain

The primary objective of this study was to investigate the energy recovery performance of the permafrost hydrate deposit in the Qilian Mountain at site DK-2 using depressurization combined with thermal injection by the approach of numerical simulation. A novel multi-well system with five horizontal wells was applied for large-scale hydrate mining. The external heat is provided by means of water injection, wellbore heating, or the combinations of them through the central horizontal well, while the fluids are extracted outside from the other four production wells under constant depressurization conditions. The injected water can carry the heat into the hydrate deposit with a faster rate by thermal convection regime, while it also raises the local pressure obviously, which results in a strong prohibition effect on hydrate decomposition in the region close to the central well. The water production rate is always controllable when using the multi-well system. No gas seepage is observed in the reservoir due to the resistance of the undissociated hydrate. Compared with hot water injection, the electric heating combined with normal temperature water flooding basically shows the same promotion effect on gas recovery. Although the hydrate regeneration is more severe in the case of pure electric heating, the external heat can be more efficiently assimilated by gas hydrate, and the efficiency of gas production is best compared with the cases involving water injection. Thus, pure wellbore heating without water injection would be more suitable for hydrate development in deposits characterized by low-permeability conditions.     

Study on Hydrate Production Behaviors by Depressurization Combined with Brine Injection in the Excess-Water Hydrate Reservoir

Depressurization combined with brine injection is a potential method for field production of natural gas hydrate, which can significantly improve production efficiency and avoid secondary formation of hydrate. In this work, the experiments of hydrate production using depressurization combined with brine injection from a simulated excess-water hydrate reservoir were performed, and the effects of NaCl concentration on hydrate decomposition, temperature change, and heat transfer in the reservoir were investigated. The experimental results indicate that there is little gas production during depressurization in a excess-water hydrate reservoir, and the gas dissociated from hydrate is trapped in pores of sediments. The high-water production reduces the final gas recovery, which is lower than 70% in the experiments. The increasing NaCl concentration only effectively promotes gas production rate in the early stage. The final cumulative gas production and average gas production rate have little difference in different experiments. The NaCl concentration of the produced water is significantly higher than that which is in contact with hydrate in the sediments because the water produced by hydrate decomposition exists on the surface of undissociated hydrate. The high concentration of NaCl in the produced water from the reactor significantly reduces the promoting effect and efficiency of NaCl solution on hydrate decomposition. The injection of NaCl solution decreases the lowest temperature in sediments during hydrate production, and increases the sensible heat and heat transfer from environment for hydrate decomposition. The changes of temperature and resistance effectively reflect the distribution of the injected NaCl solution in the hydrate reservoir.     

注气驱替煤层气数值模拟

建立一种注气驱替煤层气的双重介质数学模型,考虑注气驱替煤层气中多组分气体渗流、吸附/解吸、扩散及孔隙度和渗透率敏感性等多物理场的耦合,用有限差分方法对数学模型数值求解,并验证模型的有效性.通过实例模拟,对比分析注入CO₂、N₂和70%N₂+30%CO₂提高采收率、产出组分动态及储层物性.计算表明:注入CO₂、N₂及其混合气体均能显著提高煤层气藏采收率,提高程度可达28%以上;N₂在注入后迅速突破产出,而CO₂突破时间较晚;注气后基质的收缩/膨胀效应在孔隙度和渗透率敏感性中起主导作用,CO₂吸附造成孔隙度和渗透率减小,而N₂吸附将增大孔隙度和渗透率.     

Numerical Investigation into the Development Performance of Gas Hydrate by Depressurization Based on Heat Transfer and Entropy Generation Analyses

The purpose of this study is to analyze the dynamic properties of gas hydrate development from a large hydrate simulator through numerical simulation. A mathematical model of heat transfer and entropy production of methane hydrate dissociation by depressurization has been established, and the change behaviors of various heat flows and entropy generations have been evaluated. Simulation results show that most of the heat supplied from outside is assimilated by methane hydrate. The energy loss caused by the fluid production is insignificant in comparison to the heat assimilation of the hydrate reservoir. The entropy generation of gas hydrate can be considered as the entropy flow from the ambient environment to the hydrate particles, and it is favorable from the perspective of efficient hydrate exploitation. On the contrary, the undesirable entropy generations of water, gas and quartz sand are induced by the irreversible heat conduction and thermal convection under notable temperature gradient in the deposit. Although lower production pressure will lead to larger entropy production of the whole system, the irreversible energy loss is always extremely limited when compared with the amount of thermal energy utilized by methane hydrate. The production pressure should be set as low as possible for the purpose of enhancing exploitation efficiency, as the entropy production rate is not sensitive to the energy recovery rate under depressurization.     

不同笼占据率Ⅰ型甲烷水合物结构和光学性质的第一性原理研究

本文基于第一性原理计算,对三种不同结构的Ⅰ型甲烷水合物进行弛豫,得到优化后的结构、电子态密度及光学性质,通过对结果的分析揭示不同笼子占据率对水合物的结构和相关性质的影响。这三种结构分别为:(cI)只有一个大笼未被占据;(cII)只有一个小笼未被占据;(cIII)每个笼子都被甲烷分子占据。结果显示,cIII是最稳定的,因为它有完美的晶体结构;cII和cI相对较不稳定,其中cI在缺失一个甲烷分子的情况下,结构出现了较大的变形,这导致它成为三种情况中最不稳定的结构;相反,同样缺失了一个甲烷分子的cII的结构变形就很小。cII和cI的体积变化分别是0.56%和2.1%,cII的电子态密度和能带几乎与cIII的一致,而cI的则与前两者差别很大。计算结果表明,相对于电子转移,质子无序对水合物的介电常数的影响更为主要;甲烷水合物只对紫外光有响应,无论结构和占据率差异如何,甲烷水合物都具有相近的光学性质。本文的结果证明,缺失一个甲烷分子,对cII造成的影响很小,其晶体结构、介电常数和光学性质与cIII的一致,然而同样缺失一个甲烷分子的cI的结构及性质却出现了巨大变化。这些结果可为水合物探测提供有价值的参考。     

TBAB‐CO2水合物形成过程的微观实验

四丁基溴化铵（TBAB）半笼型水合物在二氧化碳（CO₂）捕集和封存技术中具有巨大的发展与应用潜力。由于晶体结构的复杂性,TBAB半笼型水合物的动力学过程尚未得到充分的研究。为了解TBAB半笼型水合物在储气方面的动力学特性,实验采用原位激光拉曼技术和多晶粉末X射线衍射仪（PXRD）对nCO₂·TBAB·26H₂O和nCO₂·TBAB·38H₂O水合物的光谱特征进行了鉴别与分析,利用原位激光拉曼技术考察了CO₂分子分别进入2种晶体结构的动力学过程。研究结果表明,2种晶体结构的拉曼光谱具有较高的相似性,值得注意的是nCO₂·TBAB·26H₂O中位于1 309.5和1 326.9 cm-1的拉曼峰为TBA+阳离子中C-C键的变形振动峰,在nCO₂·TBAB·38H₂O水合物中峰基本不发生改变,但半峰宽降低,峰形也变得相对清晰;同时,nCO₂·TBAB·26H₂O中位于1 446.6和1 458 cm-1的拉曼峰为TBA+阳离子中C-H键的剪切振动峰,在nCO₂·TBAB·38H₂O水合物中分别向左、右两边发生了位移,峰形的重叠度也随之下降。依据上述2处拉曼光谱特征可以对2种晶体结构进行辨别。通过PXRD图谱可以发现2种晶体结构的衍射图谱存在着比较明显的差距。nCO₂·TBAB·26H₂O晶体属于四方晶系,空间群(P4/m),而nCO₂·TBAB·38H₂O属于正交晶系,空间群(Pmma)。图谱中2θ=8.406°和10.941°分别为nCO₂·TBAB·38H₂O的(200)和(220)晶面的特征峰,而2θ=5.976°和6.969°分别为nCO₂·TBAB·26H₂O的(012)和(003)晶面特征峰,可以用来判别样品中水合物的晶体结构。在原位拉曼测量过程中,nCO₂·TBAB·26H₂O和nCO₂·TBAB·38H₂O分别在已经合成好的TBAB·26H₂O和TBAB·38H₂O水合物表面形成。在276 K,2 MPa条件下,气相中的CO₂分子分别进入2种晶体结构中用于储气的512笼形结构,在1 275.4和1 379.3 cm-1处形成特征峰并逐渐增长。实验以2种TBAB水合物位于1 110.3 cm-1的拉曼峰作为参考,比较了CO₂在水合物中的增长速率。研究发现在反应初期的75 min内CO₂在2种水合物中的含量基本保持线性增长且上升速率的差别不大。由于测量点位于水合物表面,受气体在水合物中扩散的阻力较小同时2种TBAB水合物均采用512笼形结构储气导致了储气速率相近。以上的微观晶体结构研究结果对TBAB水合物法捕集和封存CO₂技术应用具有重要的意义。     

聚合物充填过程中裹气现象的数值模拟

针对聚合物充填过程中的裹气现象,采用一种有限元（FEM）-间断有限元（DG）耦合算法对其进行数值模拟。对于自由运动界面,采用水平集（Level Set）方法进行捕捉;用XPP（eXtended Pom-Pom）本构模型来描述黏弹性流体的流变行为。采用有限元-间断有限元耦合算法求解统一的流场方程,并采用隐式间断有限元求解XPP本构方程、Level Set及其重新初始化方程。数值结果与文献中的实验结果及模拟结果吻合较好,验证了数值方法的稳定性及准确性。分析带有非规则嵌件型腔内,注射速度及浇口尺寸对裹气现象的影响,裹气容易出现在较高注射速度及较小浇口的情形。