南海海泥中甲烷水合物的形貌及赋存特性

水合物表观形貌受水合物的生长方式影响,能够反映水合物在沉积物中的分布以及与沉积物的空间关系,进而对含水合物沉积物的物理特性产生影响。本文通过在实际钻采的南海神狐海域水深2713m的海泥中生成甲烷水合物,利用冷冻扫描电子显微镜（Cryo-SEM）和能谱仪（EDS）对合成水合物的微观形貌、元素组成进行表征。结果表明,与冰相比,纯水体系下的甲烷水合物形貌单一且容易分解。纯水体系生成的水合物与海泥体系生成的水合物形貌相似,均呈颗粒胶结状,微量纳米级别的颗粒冰分布在表面。元素分析表明相较于纯水体系,海泥中生成的水合物C元素含量更高,水合物笼子占有率也越高。海泥中含有微量的C元素,通过C元素含量增加及C、Si比提高确定了表面颗粒胶结状为水合物。本研究为辨别沉积物中的水合物提供了新思路,为研究水合物的表观形貌及赋存提供了重要方法。     

TBAB水合物晶体生长过程的实验研究

通过对常压下9%(w) TBAB溶液降温生成水合物晶体的过程进行观察,以过冷度作为生长驱动力,研究了TBAB水合物晶体的生长特性. TBAB水合物刚形成时,晶体呈高透光度及规则柱体外形,随晶体继续生长逐渐变得不规则,透光度下降. 当恒温浴的过冷度分别为6.0, 8.1和9.6 K时,水合物晶体长度/宽度方向生长时间依次为183 min/140 min, 85 min/65 min, 70 min/37 min,同时反应前的等待时间即生成时间分别为83, 53和55 min. 生长时间和生成时间随过冷度增加逐渐降低,幅度逐渐减小,表明过冷度增加能有效减少水合反应时间,促进水合物的快速生成. 过冷度增加会增加TBAB水合物晶体成核数量,因此晶体与溶液的总体接触面积增加,有利于水合物的快速形成.     

热力法开采天然气水合物的模拟实验研究

在天然气水合物一维开采模拟系统上进行了模拟热力法开采天然气水合物的实验研究. 使用甲烷气体与NaCl溶液在一定温度和压力条件下形成水合物. 通过以不同速率注入不同温度的热水,研究了热力法开采水合物过程中含水合物沉积物的温度分布以及甲烷气体、水生产规律. 结果表明,在整个分解过程中,气体生产速率随时间增加而增加,直到达到最大值后开始下降,而水生产的速率几乎保持恒定. 通过对实验结果的能量分析表明,热力开采的能量效率在0.38~2.59之间. 注入热水的温度、速率以及沉积物中水合物的饱和度对热力法开采水合物的能量效率有重要影响.     

含盐蒙脱石中甲烷水合物的生成/分解特性及离子分布研究

目前,天然气水合物成藏和开采是新能源开发应用的热点,但海域沉积物中天然气水合物的形成/分解特性,及盐离子对水合物稳定性的影响等关键问题亟待解决。利用天然气水合物原位取样技术对甲烷水合物在含盐多孔介质中生成和分解过程进行原位扫描电镜(Scanning Electron Microscopy, SEM)测试和能谱分析(Energy Dispersive Spectrometry, EDS),系统研究了含0.5 mol/L NaCl溶液的蒙脱石中甲烷水合物生成、分解过程中形貌的变化及离子分布特征。研究发现水合物生成和分解过程元素分布发生明显改变,水合物生成的排盐效应使得NaCl在水合物颗粒与颗粒交结处以水合盐离子的形成存在,并且Na+和Cl-在蒙脱石表面分层排布。水合物生成后蒙脱石表面呈独立颗粒状,水合物分解后蒙脱石表面凹陷并形成微小的气体通道,并且水合物分解后蒙脱石的骨架堆积结构发生改变。研究得出水合物成核、生长、分解过程均在特定基元颗粒间是独立进行的,并且生长与分解过程与水合物晶胞结构有关。     

气水体系甲烷水合物生成和分解动力学

为进一步探明搅拌对甲烷水合物生成和分解动力学特性的影响,借助容积约为522mL,最高操作压力21MPa的高压全透明反应釜装置,开展了不同搅拌条件下甲烷水合物的生成、分解和浆液流动实验,得到了搅拌对水合物生成量、生长速率和分解速率的影响规律,基于搅拌电机扭矩值分析了不同搅拌速率下水合物浆液的流动特性。搅拌电机型号ViscoPakt Rheo-57,带有扭矩测量功能,测量最大范围57N·cm,精度±0.04N·cm。结果表明：在水合物开始快速生成的前期,水合物的最大生成量、最大生长速率及平稳生长速率都随搅拌速率的增大而增大,进一步验证了传质是控制水合物生成过程的首要因素;在水合物分解阶段,搅拌能提高水合物颗粒的分散性,促进分解气的运移产出;此外,不同搅拌速率下,水合物浆液的电机扭矩随着水合物体积分数的增大都呈现先保持平稳再逐渐增大最后剧烈波动的规律,由此得到了水合物浆液携带固相颗粒的临界体积分数。研究结论在一定程度上揭示了水合物的生长和分解机理,为动力学预测模型研究提供了参考。     

温度对多孔介质中甲烷水合物生成过程的影响

采用自行设计的实验装置,分别进行了0℃以上(274.7 K)、0℃附近(272.8±0.5 K)和0℃以下(267.4 K)3种不同温度下,在20～40日石英砂中甲烷水合物的生成实验.结果表明甲烷水合物在0℃以上生成比较快;在0℃附近储气量大,水合物在整个砂层中的分布比较均匀.针对实验结果,本文提出了水合物在三种不同温度下的生成机理.     

外部剪切对天然气水合物生成影响的实验研究

未来对于天然气的运输、调峰以及储存等领域,天然气水合物都会起到重要的作用,天然气水合物应用技术的关键在于天然气水合物的快速及大量生成。因此,对天然气水合物生成过程做进一步研究很有必要。目前,人们主要研究了温差、压力扰动、降温速度等因素对水合物生成过程的影响作用,但基于剪切作用对水合物生成的研究还不够深入。因此,实验研究了在含动力学抑制(PVPK90)的条件下,有无剪切作用对CH4水合物生成量的影响。结果表明:剪切作用会增加天然气与水分子的碰撞几率,促进水合物晶核的生成和成长,但同时会阻碍水合物晶核微粒的聚结作用。一定体积的溶液下,形成的水合物晶核微粒数量受到限制。在剪切作用被消除后,内壁上会聚结并附着大量水合物晶核,并为新的水合物晶核形成提供空间。因此,使甲烷水合物晶核的形成过程与聚结过程在两个连通的容器中同时进行,则水合物的形成过程不会被阻止。更换水合物晶核聚结的容器,则工业上能够大量生成用于储存运输天然气的水合物。     

量热法多孔沉积物内CH4水合物生成过程中的放热行为

掌握天然气水合物在多孔沉积物生成过程中的放热规律对于天然气水合物的资源开发和了解水合物的成藏规律都具有重要意义。本研究通过高压微量热仪考察了石英砂粒径、初始含水率、温度及含盐条件对CH₄水合物在多孔沉积物内生成过程中放热行为的影响。实验结果表明,随着石英砂粒径的减小,水合物生成的放热速率随之增加。随着初始含水率的降低,水合物的放热峰明显增大,但在实验考察时间内,最终的累积放热量和含水率并没有呈现出明显的相关性。当温度在263.15K时,CH₄水合物生成过程中不存在明显的放热。对于在3.35% NaCl盐溶液体系中进行的甲烷水合物生长放热实验,发现其放热规律与在纯水体系下的放热规律具有较高的一致性,但其总体放热速率和累积放热量较纯水体系更低。实验结果呈现了良好的规律性,对进一步开发量热仪在水合物生成动力学方面的应用具有一定的参考价值。     

流动状态对甲烷水合物生成速率影响的研究

为了研究流动状态对甲烷在油包水乳液中降压形成水合物过程的影响,在温度为273.35 K,初始压力为6.80 MPa的条件下,进行了一系列不同搅拌速度下甲烷水合物的生成实验。实验结果表明,各组反应的水合物初始形成压力基本一致,诱导时间的长短无规律性。随着搅拌转速的增大,甲烷气体的吸收速度和水合物的生成速度均随之增大。但到达700 r/min后,搅拌转速的继续增加对吸收和水合过程的影响作用并不明显。     

石英砂中甲烷溶解运移体系水合物生成与聚集实验分析

建立了可模拟海底天然气水合物形成环境的大型三维成藏实验模拟装置,其主体高压反应釜内径500 mm,高1000 mm。在此基础上,采用填砂模型,进行了甲烷溶解运移体系下甲烷水合物生成与聚集过程的实验模拟分析。实验流程为：甲烷溶解于NaCl溶液中,再泵送进入高压反应釜,在沉积层中渗流并生成甲烷水合物。通过30个电阻率传感器监测甲烷水合物的生成和聚集过程。实验结果表明,甲烷溶解运移体系下甲烷水合物生成之后首先分散在溶液中,当溶液的总甲烷浓度（溶解的甲烷及水合物分散相中的甲烷）达到操作条件下盐溶液体系甲烷饱和溶解度后,甲烷水合物从溶液中析出。电阻率分布实验结果表明,析出甲烷水合物的聚集区域受溶液流动控制。     

甲烷水合物分解过程的微尺度测量

实验采用激光拉曼和X射线粉末衍射(PXRD) 在253 K，常压条件下对甲烷水合物的分解过程分别进行了原位测量。研究发现，位于表层的甲烷水合物在前30～50 min内发生分解并生成Ⅰh冰相，随后表层冰相对内层水合物相的包覆引起了“自保护”效应的产生并导致甲烷水合物分解速率显著降低。分解过程中，甲烷在水合物大小笼中的含量之比始终保持在3.2左右，同时水合物晶面特征峰峰面积也按照相同的曲线下降，表明甲烷水合物以晶胞为单位进行整体分解。Ⅰh冰的各个晶面特征峰峰面积差异化的增长曲线表明形成的Ⅰh冰相倾向于片状生长，有助于在水合物表面生成一层冰膜，进而产生“自保护”效应。     

Effect of surface curvature and wettability on nucleation of methane hydrate

Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.     

Kinetic and Phase Behaviors of Catalytic Cracking Dry Gas Hydrate in Water-in-Oil Emulsion

The systematic experimental studies were performed on the hydrate formation kinetics and gas-hydrate equilibrium for a simulated catalytic cracking gas in the water-in-oil emulsion. The effect of temperature, pressure and initial gas-liquid ratio on the hydrate formation was studied, respectively. The data were obtained at pressures ranging from 3.5 to 5 MPa and temperatures from 274.15 to 277.15 K. The results showed that hydrogen and methane can be separated from the C₂₊ fraction by forming hydrate at around 273.15 K which is much higher temperature than that of the cryogenic separation method, and the hydrate formation rate can be enhanced in the water-in-oil emulsion compared to pure water. The experiments provided the basic data for designing the industrial process, and setting the suitable operational conditions. The measured data of gas-hydrate equilibria were compared with the predictions by using the Chen-Guo hydrate thermodynamic model.     

Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas–water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.     

Enhanced hydrate formation under mild conditions using a novel spiral-agitated reactor

Hydrate-based solidified natural gas (SNG) technology provides a promising approach to store and transport natural gas, but demanding formation conditions and low methane storage capacity limit its application. Here, we presented a novel spiral-agitated reactor, and hydrate formation in pure water and amino acid systems was evaluated. It is worth to highlight that spiral agitation significantly enhances initial hydrate grow kinetics, and satisfied methane uptake of 134.9 V/V was obtained under a mild condition (4.3 MPa, 275.15 K, and 30 rpm). Impressively, when amino acids were introduced, late hydrate growth was greatly improved because of secondary uptake, and a large methane uptake (145.97 V/V) was obtained under a milder condition (3.8 MPa, 275.15 K, and 60 rpm), which increases by 82.97% comparing to that in pure water systems. These findings provide a new insight (synergistic effect of spiral agitation and amino acids) on enhanced hydrate production under extremely mild conditions.     

甲烷+氨水体系水合物生成条件实验测定及计算

甲烷在氨水体系中生成水合物的实验数据对于开发水合法回收合成氨驰放气工艺以及操作条件的确定具有重要意义。本文测定了氨摩尔分数为1.018、3.171、5.278氨水溶液中甲烷气体水合物的生成条件。结果表明：氨的加入对甲烷水合物的生成起着明显抑制作用,而且随着氨浓度的增加,生成压力越高。采用Chen-Guo模型对甲烷在氨水中生成水合物的数据进行了计算,得到了较为满意的计算结果,平均误差为2.71%,说明Chen-Guo模型能够较好地预测该类体系的水合物的生成条件。     

Migration of a single gas bubble in water during the formation of stable gas-hydrate crust on its surface

A theoretical model of gas-hydrate formation during the migration of the methane bubble in water under thermobaric conditions of hydrate stability has been considered. Numeric solutions were obtained and analyzed for two limiting cases when the rate of formation of the hydrate crust on bubble surface is constrained by the intensity of heat removal, which is released during hydrate-formation process by the surrounding water or the diffusive resistance of gas hydrate crust against the transfer of hydrate-forming components. A comparative analysis of the numeric results with the experimental data showed that the diffusive transfer of hydrate-forming components through the crust most adequately described the process of hydrate-particle growth that was observed in experiments during the ascent of methane particles in seawater. The conditions of the best agreement between the theoretical and experimental data on changing of radius of gas-hydrate particle allowed numeric estimates to be obtained for values of the reduced coefficient of gas and water diffusion through the hydrate crust.     

Methane Hydrate Formation and Dissociation in the presence of Bentonite Clay Suspension

The present work reports the effect of bentonite clay on methane hydrate formation and dissociation in synthetic seawater of salinity 3.55 % of total dissolved salts. Extensive observations of pressure‐temperature equilibrium during formation and decomposition of methane hydrate under different conditions have been made. It is observed that phase equilibrium conditions of hydrate are affected on changing the concentration of bentonite clay in synthetic seawater. Induction time for hydrate nucleation has been measured under different concentrations of clay and subcooling conditions. The presence of bentonite clay in synthetic seawater reduces the induction time of hydrate formation. Enthalpy of hydrate dissociation is calculated by Clausius‐Clapeyron equation using measured phase equilibrium data. The amount of gas consumed during hydrate formation has been calculated using real gas equation. It is found that a larger amount of gas is consumed upon addition of bentonite clay in synthetic seawater.     

Influence factors of methane hydrate formation from ice: Temperature,pressure and SDS surfactant

A series of experiments of forming hydrate from ice powders in different conditions have been carried out with constant volume method to evaluate the influence factors such as pressure, temperature, and SDS surfactant. The change of temperature and pressure were collected as a function of elapsed time, which were used to calculate the gas consumption and hydrate saturation during hydrate formation (pVT method). Based on the experimental results and the analysis, it is concluded that: (1) Both initial pressure and temperature have effect on the hydrate formation and temperature plays a more important role in the process; (2) heating and secondary pressurization will promote the gas hydrate formation and enhance the hydrate saturation as a result. Meanwhile, the promotion of heating seems to be more obvious than that of secondary pressurization; (3) different concentrations of SDS surfactant have clearly influence on the saturation of gas hydrate and there is an optimal concentration to promote the hydrate formation.