降温模式对甲烷水合物形成的影响

在定容条件下,以两种不同的降温模式(缓慢降温和快速降温)进行甲烷水合物在沉积物中的形成实验. 结果表明,甲烷水合物在沉积物中的形成过程包括气液溶解、核化、生长、稳定4个阶段. 在相同的初始条件下,降温模式对水合物生成的热力平衡影响较小,但对水合物生成动力学有显著改变. 快速降温下水合物生长速度明显快于缓慢降温,随着水合物初始条件不同,缓慢降温比快速降温水合物形成时间约增加21.4%~28.8%.     

Effect of surface roughness on methane hydrate formation and its implications in nucleation design

As a new form of energy with substantial potential, natural gas hydrate will play a crucial strategic role in the future due to its vast reserves and broad industrial application prospects. To better comprehend the nucleation and growth mechanism of clathrate hydrate, an enhanced thermodynamic model was proposed based on the wall roughness model and nucleation theory. In general, we discovered that the nucleation of hydrate on a smooth wall surface conforms to the conclusion of classical nucleation theory. However, curvature and surface roughness are frequently characterized by hydrophilicity's inhibition of hydrate and hydrophobicity's enhancement. The specific situation is more complex and requires specific analysis and discussion. Nonetheless, this also explains the uneven distribution of hydrate nucleation induction time. Our research reveals a fundamental method for designing or manipulating the heterogeneous nucleation of hydrates. We foresee promising applications in hydrate-related technologies based on the fractal structure of the substrate's surface.     

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.     

Nucleation of methane hydrate and ice in emulsions of water in crude oils and decane under non-isothermal conditions

Achievable supercooling for the formation of methane hydrate from water emulsions was studied in seven different crude oils and in decane. The experiments were performed under constant rate cooling from + 20 to-15 °C and a pressure of methane of 12 MPa. It was demonstrated that the shapes and positions of the resulting survival curves depend on the density, viscosity and dispersive power of oil samples used in the experiments, as well as on the degree of oil oxidation. In addition, results of the experiments on ice freezing under the same emulsions are presented. The results obtained in the work allowed us to discuss the possibility and features of primary and secondary nucleation of the hydrate and ice in the systems under consideration.     

动力学抑制剂与乙二醇协同作用下甲烷水合物再生成

在500mL的高压反应釜中,实验研究了乙二醇（MEG）与动力学抑制剂PEO-co-VCap-1在细砂存在下对甲烷水合物再生成过程的协同抑制作用。实验过程中,控制MEG的质量分数范围为0~5%,PEO-co-VCap-1的质量分数范围为0~0.5%,形成4种的抑制剂配伍组合,进行了12组实验。实验结果表明,PEO-co-VCap-1在单独作用时,可以延缓水合物的成核阶段,但可能导致水合物在生长阶段短时间内大量生成的灾难性生长现象。其与MEG复配可在延缓水合物成核的同时,有效减少灾难性增长现象的出现,降低油气管输的堵管风险。当MEG质量分数为5%、PEO-co-VCap-1质量分数为0.5%时,协同抑制效应极为明显,可将甲烷水合物诱导期延长至2800min以上。MEG同PEO-co-VCap-1的协同抑制效果与提高温度的抑制作用相似。这一发现表明,如果在使用PEO-co-VCap-1的同时使用MEG等良好的增效剂,有助于动力学抑制剂用于更高的过冷度环境,为高效解决高过冷条件下油气生产中的水合物防控问题提供新的可能。     

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。     

离子对甲烷水合物相平衡的影响

自由水盐度直接影响水合物的生成和分解,为了充分研究自由水盐度对甲烷水合物相平衡的影响,本文利用正交实验设计方法研究了不同离子组成和浓度条件下多孔介质中水合物形成与分解特性。运用正交法研究水合物可减少实验次数、缩短实验周期。甲烷水合物相平衡点通过定容压力搜索法测得。与纯水体系相比,添加离子后相同压力条件下甲烷水合物的平衡温度降低,并且随着离子浓度的增加,平衡温度进一步降低。方差分析证明阳离子中Mg²⁺对水合物平衡影响最显著;极差分析结果表明,阳离子的影响程度从大到小依次为Mg²⁺、Ca²⁺、Na⁺、K⁺。SO^2-₄、CO^2-₃、Cl^-三种阴离子浓度对水合物相平衡点影响均显著。水合物诱导时间变化无明显规律,受离子种类、浓度影响不显著。     

聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究

注入动力学抑制剂是一种有效缓解天然气水合物管道堵塞的方法。本文以动力学抑制剂聚乙烯基己内酰胺(PVCap)结构为基础,将氧乙基和酯基引入PVCap的分子链端,合成了新抑制剂PVCap-XA1,在高压定容反应釜内评价了PVCap-XA1对甲烷水合物形成的抑制作用,并采用粉末X射线衍射、低温激光拉曼光谱和冷冻扫描电子显微镜研究了抑制剂对甲烷水合物结构和形态的影响。实验结果表明,相同实验条件下PVCap-XA1比PVCap具有更好的抑制作用;微观测试表明PVCap-XA1的加入没有改变甲烷水合物的晶体结构,但会使甲烷水合物晶面扭曲变形,可以降低水合物大小笼占有比(I_L/I_S),使得甲烷分子更难进入水合物大笼,同时PVCap-XA1的加入使甲烷水合物的微观形貌由多孔有序变得更致密而不利于气体通过。     

Fundamental challenges to methane recovery from gas hydrates

The growing use of natural gas, cleanest of all available fossils fuels, is already raising concern regarding the long-term supply of this precious resource. The amount of methane in gas hydrates is much greater than all other presently known sources of methane. This paper describes some fundamental challenges, the location, magnitude, and feasibility of recovery, which must be addressed to recover methane from dispersed hydrate sources. For methane recovery, we briefly describe kinetic models of methane hydrate decomposition for temperature and pressure conditions that mimic in situ methane hydrate stability. We also propose the catalytic role of sediment impurities, if any, in inducing nucleation sites for hydrate formation. The availability of plentiful methane is important to avoid future energy crises, such as that which crippled the world economy three decades ago.     

蜡晶析出对CO2水合物相平衡及诱导特性的影响

为了探明蜡晶析出对水合物生成相平衡特性及成核特性的影响,本文选用2^#工业白油与60^#昆仑石蜡的混合溶液来模拟含蜡体系,利用高压可视化搅拌釜开展含蜡体系水合物生成实验,结合水合物生成过程中的可视化图像,研究不同蜡晶浓度对水合物生成相平衡曲线、水合物成核诱导时间、诱导时间变化率的影响规律及蜡晶析出对水合物生成机理的影响。结果表明：①随着蜡晶浓度的增加,水合物生成相平衡条件逐渐降低,相平衡曲线较无蜡体系向右偏移,且蜡晶浓度越大,偏移趋势越明显,在温度281.5K时,3.5%（质量分数）的蜡含量比无蜡体系的相平衡压力降低6.5%;②通过分析不同蜡晶浓度对水合物成核诱导时间的影响发现,蜡晶析出加快了水合物结晶,缩短了水合物成核诱导时间,且蜡晶浓度越大,诱导时间缩短越明显;③通过探究不同蜡晶浓度对水合物成核诱导能力的影响发现,随着蜡晶浓度的增加,蜡晶析出对水合物诱导成核的促进能力总体呈现先增大后减小的趋势,即蜡晶对水合物的促进能力不是无限增大的,会随蜡晶浓度的增加逐渐减弱;④通过分析蜡晶析出对水合物生成速率及生成位置的影响发现,当体系达到水合物生成条件时,反应釜中心部分的水合物会先于气液表面及釜壁生成。本文研究成果有助于深海油气开采的应用发展,同时为更好研究蜡晶与水合物耦合特性提供可靠的pVT数据。     

全可视化反应釜内二氧化碳水合物的生成分解特征

二氧化碳水合物封存技术已成为目前碳封存研究的热点。该技术中对于二氧化碳水合物的生成分解特征及其影响因素的研究是当前的重点和难点。本文设计了高压全透明双反应釜实验平台,以高纯度二氧化碳和去离子水作为研究对象,在17℃、7MPa的初始温压条件下,进行了二氧化碳水合物的初次和二次生成分解实验,并设置对照组对搅拌的影响进行了研究,而后与甲烷在相同条件下的实验进行对比。实验结果表明,搅拌会促进二氧化碳水合物的生成,在400r/min的转速条件下,缩短诱导时间可达40%,增大压降速率可达15%,形成更多且更致密厚实的水合物,并延缓了分解;多次生成可以减少水合物的诱导时间,但对于水合物生成的总量几乎没有影响。与甲烷水合物相比,二氧化碳水合物生成的量大且更难以分解,实验结果有利于二氧化碳的海洋水合物封存技术的开发应用。     

0℃以下含SDS的甲烷水合物生成方式及过程对其分解速率的影响

The dissociation rates of methane hydrates formed with and without the presence of sodium dodecyl sulfate(methane-SDS hydrates),were measured under atmospheric pressure and temperatures below ice point to investigate the influence of the hydrate production conditions and manners upon its dissociation kinetic behavior.The experimental results demonstrated that the dissociation rate of methane hydrate below ice point is strongly dependent on the manners of hydrate formation and processing.The dissociation rate of hydrate formed quiescently was lower than that of hydrate formed with stirring;the dissociation rate of hydrate formed at lower pressure was higher than that of hydrate formed at higher pressure;the compaction of hydrate after its formation lowered its stability,i.e.,increased its dissociation rate.The stability of hydrate could be increased by prolonging the time period for which hydrate was held at formation temperature and pressure before it was cooled down,or by prolonging the time period for which hydrate was held at dissociation temperature and formation pressure before it was depressurized to atmospheric pressure.It was found that the dissociation rate of methane hydrate varied with the temperature(ranging from 245.2 to 272.2 K) anomalously as reported on the dissociation of methane hydrate without the presence of surfactant as kinetic promoter.The dissociation rate at 268 K was found to be the lowest when the manners and conditions at which hydrates were formed and processed were fixed.     

Dual Effect of Low‐Dosage Poly(Ethylene Oxides) on Methane Hydrate Formation

Time‐dependent isochoric formation of methane hydrate was investigated in the presence of low‐dose poly(ethylene oxides) (PEOs). The effect of different molecular weights of PEO on methane hydrate nucleation time and storage capacity was studied and compared. Kinetic measurements revealed a dual effect of PEO, including inhibition and stabilization effects, on methane hydrate formation. The nature and type of the effect arises from the difference in molecular weights and concentration ranges of PEOs. These parameters directly affect the nucleation time and storage capacity of methane hydrate. Generally, in comparison with pure water, PEO improved the storage capacity of methane hydrate. PEO (1000 kD) at a concentration of 0.5 wt % exhibits a significant kinetic inhibitory performance. However, it was an efficient low‐dosage hydrate stabilizer at a concentration of 0.25 wt %, along with producing gas‐rich methane hydrate suitable for gas fuel storage and transportation.     

The modelling of hydrocarbon bubble plumes to include gas hydrate formation

Information gained on hydrate formation on a single rising bubble of hydrocarbon gas is applied to the case of a complete bubble plume. When hydrate formation is included in the plume equations there is a strong coupling between small scale bubble behaviour and the total plume buoyancy. The sensitiv of the plume solutions to this coupling is examined for methane and a natural gas typical of certain Arctic oilwells. The results of the latter are app to a hypothetical oilwell blowout under Arctic conditions, and indicate that for wellhead depths greater than 800 m all the gas will be converted to hy before the surface is reached.     

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。     

Synthesis and evaluation of poly (N-vinyl caprolactam)-co-tert-butyl acrylate as kinetic hydrate inhibitor

Low dosage kinetic hydrate inhibitors (KHIs) are a kind of alternative chemical additives to high dosage thermodynamic inhibitors for preventing gas hydrate formation in oil & gas production wells and transportation pipelines. In this paper, a new KHI, poly (N-vinyl caprolactam)-co-tert-butyl acrylate (PVCap-co-TBA), was successfully synthesized with N-vinyl caprolactam (NVCap) and tert-butyl acrylate. The kinetic inhibition performances of PVCap-co-TBA on the formations of both structure I methane hydrate and structure II natural gas hydrate were investigated by measuring the onset times of hydrate formation under different conditions and compared with commercial KHIs such as PVP, PVCap and inhibex 501. The results indicated that PVCap-co-TBA outperformed these widely applied inhibitors for both structure I and structure II hydrates. At the same dosage of KHI, the maximum tolerable degree of subcooling under which the onset time of hydrate formation exceeded 24 hours for structure I hydrate was much lower than that for structure II hydrate. The inhibition strength increased with the increasing dosage of PVCap-co-TBA; The maximum tolerable degree of subcooling for the natural gas hydrate is more than 10 K when the dosage was higher than 0.5% (mass) while it achieved 12 K when that dosage rose to 0.75% (mass). Additionally, we found polypropylene glycol could be used as synergist at the dosage of 1.0 % (mass) or so, under which the kinetic inhibition performance of PVCap-co-TBA could be improved significantly. All evaluation results demonstrated that PVCap-co-TBA was a very promising KHI and a competitive alternative to the existing commercial KHIs.     

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。     

Experimental investigation and modeling on the dissociation conditions of methane hydrate in clayey silt cores

As the majority of global natural gas hydrate reserve, the dissociation conditions of hydrate in clayey silts are of great significance for its efficient production. In this work, the dissociation conditions of methane hydrate in clayey silt cores were experimentally measured by step-heating method at the temperature range of 280.76–289.55 K and pressure range of 8.11–15.03 MPa, respectively. Various cores including quartz powder, montmorillonite, and South China Sea sediments at the water content range of 20%–33% were used for investigation. The results showed that the dissociation temperatures of methane hydrate in clayey silt cores depressed compared to bulk hydrate. The grain size, salinity, and lithology of clayey silt cores significantly affect the dissociation conditions of hydrate. In comparison to grain size, salinity, and lithology had a more significant influence on the equilibrium temperature depression. The dissociation temperature depression of methane hydrate was considered as a consequence of the water activity depression which is caused by the effect of capillary, salt, or clay. A water activity meter was used to measure the water activity in clayey silt cores. The influence of salt component and mineral characteristics on the water activity was investigated. By combining the measured water activity data with the Chen-Guo model, a novel water activity measurement (WAM) method for the hydrate dissociation conditions prediction was proposed. With the maximum deviation less than 12%, the predicted results are in good agreement with the experimental data. It demonstrated that the WAM method could effectively predict the dissociation conditions of methane hydrate in clayey silts with convenience and accuracy.     

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.     

Investigation of the methane hydrate surface area during depressurization-induced dissociation in hydrate-bearing porous media

The surface area of hydrate during dissociation in porous media is essentially important for the kinetics of hydrate dissociation. In this study, the methane hydrate surface area was investigated by the comparison results of experiments and numerical simulations during hydrate decomposition in porous media. The experiments of methane hydrate depressurization-induced dissociation were performed in a 1D high pressure cell filled with glass beads, an improved and valid 1D core-scale numerical model was devel-oped to simulate gas production. Two conceptual models for hydrate dissociation surface area were pro-posed based on the morphology of hydrate in porous media, which formed the functional form of the hydrate dissociation surface area with porosity, hydrate saturation and the average radius of sand sedi-ment particles. With the establishment of numerical model for depressurization-induced hydrate disso-ciation in porous media, the cumulative gas productions were modeling and compared with the experimental data at the different hydrate saturations. The results indicated that the proposed prediction equations are valid for the hydrate dissociation surface area, and the grain-coating surface area model performs well at lower hydrate saturation for hydrate dissociation simulation, whereas at higher hydrate saturation, the hydrate dissociation simulation from the pore-filling surface area model is more reason-able. Finally, the sensitivity analysis showed that the hydrate dissociation surface area has a significant impact on the cumulative gas production.