全透明高压反应釜甲烷水合物动力学实验

水合物的生长和分解规律对开发海洋天然气水合物资源,实现深水天然气水合物气液固多相管道输送都具有重要意义。为了进一步揭示水合物的生长和分解特性,本文采用高压全透明反应釜装置,进行了温度0～30℃、压力3.35～8.16MPa和搅拌速率200～1000r/min范围内的16组甲烷水合物生长和分解动力学实验研究。结果表明：实验过程可分为水合物诱导期、快速生长期、缓慢生长期以及分解期这4个阶段。在水合物快速生长阶段,获得了温度、压力、搅拌电机扭矩和水合物生长速率随时间的变化规律,观察到了水合物颗粒的均相和非均相分布状态。通过加热促使水合物分解,揭示了分解阶段温度、压力和分解速率等关键参数的变化规律以及水合物块的分解形态。分析表明,水合物颗粒的分布状态与水合物浆液的流动性直接相关;水合物块的静态分解过程受到分解气传质控制。     

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。     

鼓泡器中环戊烷-甲烷-盐水体系水合物的生成动力学

采用鼓泡装置研究了盐水体系中环戊烷（CP）-甲烷水合物的生成动力学,分别考察了进气速率、温度、压力对水合物生成速率和进气速率对气体转化率的影响。结果显示,提高进气速率、压力,降低温度均可提高水合物生成速率。但进气速率对气体转化率有影响,进气速率过大,单位时间内进入到反应器内的气体过多,气体还未参与反应便被排出,导致气体转化率反而减小。通过观察到的实验现象,分析环戊烷-甲烷水合物的生成过程,认为水合物晶体首先在环戊烷-水界面生成,并逐步向内部气相生长,最后水合物壳破裂,气泡逸出。水合物逐渐生长成粒状,并不断聚集在一起。     

乙烯水合物在正丙醇溶液中的生成行为研究

研究了在正丙醇溶液中,压力和温度因素对乙烯水合物生成的影响。实验结果表明：压力的升高促进了水合物的生长,水合物生成速率随压力升高而加大;温度的降低促进了水合物的生长,水合物终止生成所需的时间减少,终止生成对应的压力降低。     

水合物在静态脂肪醇聚氧乙烯醚硫酸钠溶液与纯水搅拌条件下生成分析

促进天然气水合物快速大量生成是天然气水合物技术产业化的关键,因此,对其动力学促进方法进行研究是十分必要的。本文在温度为(2±0.1)℃,压力为(6.6±0.1)MPa条件下研究了不同浓度(60~1350mg/L)脂肪醇聚氧乙烯醚硫酸钠(AES)以及不同搅拌转速0~800r/min对水合物生成的影响,对两种方式的促进效果进行了对比,并从水合物生成动力学角度对AES及搅拌的促进机理进行分析。实验结果表明:AES与搅拌都可以促进液相气过饱和,加速单核生长和多核聚结过程,显著缩短诱导期,提高水合物生成速率及气体消耗量,但不同的是在水合物生长阶段搅拌仅能促进气相向液相单向移动,AES能够使气液交叉移动,显著降低了气液传质阻力,增加了成核位置,因此AES比搅拌进一步提高了水合物生成速率及气体消耗量。     

含砂搅拌体系甲烷水合物生成与分解实验研究

利用高压反应釜装置,在不同初始压力、砂粒粒径等条件下进行甲烷水合物的生成与分解实验,研究细质砂粒固相颗粒对甲烷水合物成核诱导时间、生成和分解等的影响规律。结果表明:砂粒能够促进甲烷水合物生长,体系初始压力越高,水合物生成速率越高;体系初始压力为7.2 MPa、砂粒粒径为2 000目(6.5μm)时,水合物生成过程最稳定,且水合物生成量最多;在分解过程中,纯水体系和含砂体系的分解速率相当,只存在气体释放量的差异。进而得出结论:砂粒固体颗粒的存在会促进水合物生成,所以在水合物开采过程中,若工况满足水合物生成条件,水合物二次生成会更易发生,使得矿藏砂粒、水合物、天然气、海水在管道内的多相混输堵塞风险增加;含砂条件对水合物分解的影响作用不大,矿砂在水合物分解过程中对流动安全的影响有待深入研究。该研究成果为解决深水浅层水合物开采过程中的流动安全保障问题,提供了重要的理论基础和技术支撑。     

天然气水合物生成与相平衡曲线的试验分析

通过改变动力学抑制剂、过冷度、搅拌,借助生成实验装置,分析天然气水合物的生成效果,比较以上三个条件下的天然气水合物的生成速度和生成量,进而得出以上三个变量的对天然气水合物生成效果的贡献。结果表明:增加搅拌在天然气水合物生成过程中起主要作用,其次是过冷度以及动力学抑制剂。通过对水合物生成以及分解过程中压力-温度曲线的拟合,放缓反应釜内温度的升幅,可以得到更长更精确的拟合曲线。     

近临界条件下乙烯水合物在甲醇水溶液中的生成行为研究

研究了近临界条件下乙烯水合物在甲醇水溶液中的生成行为,考察了温度、压力以及甲醇浓度对乙烯水合物生成行为的影响。实验结果表明在乙烯的近临界条件下,P-t曲线为一光滑的曲线,不易明确区分溶解阶段、成核阶段和生长阶段;随着初始压力的升高,水合物生成速率加快,且始末压差增大,水合物生成量增多;随着温度的降低,过冷度增大,促进水合物生长,压力下降速率增加,水合物生成量增多;甲醇水溶液浓度的增加,抑制了乙烯水合物的生成。     

充注压力对压缩式制冷循环连续制备CO_2水合物的影响

研制了一台能够连续制备蓄冷用CO2水合物的压缩式循环实验装置,并在该装置上研究了充注压力对水合物的预冷时间、生成质量、水合比例和潜热蓄冷量的影响。实验结果表明水合物在CO2气泡上升过程中生成,在气液界面处堆积。高的充注压力有着更理想的蓄冷特性,当充注压力为4.2 MPa时,预冷时间为8 min、水合物生成质量为8.44 kg、水合比例为75.1%、水合物潜热蓄冷量为4.22 MJ。充注压力为3.8 MPa及以上时,水合物生成量大,水合物阻碍釜内各部分的传热,使釜内中层、下层的温差较大。水合物生成过程后期,水合放热量减少,液体CO2在反应釜内的蒸发吸热效应使得釜内温度继续降低,一直到低于0℃,充注压力越高,此现象越明显。     

悬垂水滴表面天然气水合物的生长特性

针对天然气水合物的喷雾法制备,设计并搭建了悬垂水滴显微实验装置,研究了不同温度和压力条件下天然气水合物在悬垂水滴表面的生长形态,建立了水滴表面水合物膜的生长模型,并通过实验研究了驱动力、过冷度、水合反应速率、气体扩散速率及十二烷基硫酸钠(SDS)浓度对水合物膜生长的影响. 结果表明,水合物膜的生长速率随过冷度的增加而增加,实验条件下测得水滴表面水合物膜的生长率为0.24~0.39 mm/s. 水滴表面水合物膜的生长为内扩散控制,水合物的活化能为13.01 kJ/mol. 当SDS浓度为550 mg/L时,界面反应速率常数有最大值0.0027 m/s.     

Hydrate formation in oil–water systems: Investigations of the influences of water cut and anti-agglomerant

To investigate the characteristics of hydrate formation in oil–water systems, a high-pressure cell equipped with visual windows was used where a series of hydrate formation experiments were performed from natural gas + diesel oil + water systems at different water cuts and anti-agglomerant concentrations. According to the temperature and pressure profiles in test experiments, the processes of hydrate formation under two kinds of experimental procedures were analyzed first. Then, based on the experimental phenomena observed through the visual windows, the influences of water cut and anti-agglomerant on the places of hydrate formation and distribution, hydrate morphologies and hydrate morphological evolvements were investigated. Hydrate agglomeration, hydrate deposition and hydrate film growth on the wall were observed in experiments. Furthermore, three different mechanisms for hydrate film growth on the wall were identified. In addition, the influences of water cut and anti-agglomerant on the induction time of hydrate formation were also studied.     

Experimental study of hydrate formation in oil–water systems using a high-pressure visual autoclave

To investigate the characteristics of hydrate formation in oil–water systems, a high-pressure visual autoclave equipped with visual windows was used where a series of hydrate formation experiments were performed from natural gas + diesel oil + water systems at different water cuts (30 and 70%), rotation rates (100, 200, 300 r/min) and thermodynamic conditions (temperature, pressure). According to the temperature and pressure profiles in test experiments, the processes of hydrate formation under two kinds of experimental procedures were analyzed first. Then, based on the experimental phenomenon observed through the visual windows, hydrate morphologies and hydrate morphological evolvements throughout the experiments were mainly investigated. In experiments, the growth and annealing of hydrate films on the wall, the agglomeration and deposition of hydrate coated water droplets, flocculent-like hydrate deposition with water trapped in and the Pickering effect of hydrates were identified. Simultaneously, based on the experimental data of thermodynamic parameters, the kinetics of hydrate formation was studied by calculating the variations of hydrate film area and gas consumption in different experiments. In addition, the influences of temperature, pressure, and rotation rate on hydrate morphologies, hydrate morphological evolvements, and hydrate formation kinetics were also focused on.     

Quantification of the risk for hydrate formation during cool down in a dispersed oil-water system

Gas hydrates are considered a nuisance in the flow assurance of oil and gas production since they can block the flowlines, consequently leading to significant losses in production. Hydrate avoidance has been the traditional approach, but recently, hydrate management is gaining acceptance because the practice of hydrate avoidance has become more and more challenging. For better management of hydrate formation, we investigated the risk of hydrate formation based on the subcooling range in which hydrates form by associating low, medium, and high probability of formation for a gas+oil+water system. The results are based on batch experiments which were performed in an autoclave cell using a mixture gas (CH₄: C₃H₈=91.9 : 8.1 mol%), total liquid volume (200 ml), mineral oil, watercut (30%), and mixing speed (300 rpm). From the measurements of survival curves showing the minimum subcooling required before hydrate can form and hydrate conversion rates for the initial 20 minutes, we developed a risk map for hydrate formation.     

Development of a Surface‐Active Coating for Promoted Gas Hydrate Formation

This work deals with the influences of surface‐active coatings made by silanization with an increasing hydrophobicity on methane hydrate formation in view of induction times, gas uptake, and rate of gas consumption. Hydrate formation was performed in a stirred pressure autoclave under stationary and transient conditions in presence of different coatings made from diverse silanes. With increasing carbon chain length of the silanes, promoting effects were observed while using stationary formation conditions.     

凝析气井井筒水合物生成位置预测

凝析气井井筒水合物是生产过程中经常遇到的问题,本文针对某凝析气井,对水合物的形成条件进行了论述,采用水合物P-T图回归公式法对该凝析气井在不同压力条件下水合物形成的温度进行了预测,计算出了该井在不同产量条件下的井筒温度分布和压力分布,根据计算结果得知：产气量为11.98×10^4m^3/d时水合物生成温度曲线与井筒温度曲线在距离井口175m处相交,此时温度为22.8℃。若存在自由水,则从此深度到井口的油管段形成水合物。针对该凝析气井情况,建议采用加注甲醇（己二醇）和地面加热升温措施以防止水合物的形成。     

A water droplet size distribution dependent modeling of hydrate formation in water/oil emulsion

Experimental data on chord length distributions and growth rate during methane hydrate formation in water‐in‐oil emulsions were obtained in a high pressure stirring reactor using focused beam reflectance measurement and particle video microscope. The experiments were carried out at 274.2 K for 10–30% water cuts and agitation rates ranging from 200 to 500 rpm initially at 7.72 MPa. Rapid growth was accompanied by gradually decrease in rate. Free water was observed to become depleted during rapid growth while some water remained encapsulated inside hydrate layers constituting a mass transfer barrier. The apparent kinetic constants of methane hydrate formation and free‐water fractions were determined using a newly developed kinetic model independent of the dissolution rate at the gas–oil interface. It was illustrated that continued growth depends on distribution and transfer of water in oil‐dominated systems. This perception accords with observations of hydrate film growth on suspended water droplet in oil and clarifies transfer limits in kinetics. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1010–1023, 2017     

Macroscopic investigation of hydrate film growth at the hydrocarbon/water interface

Clathrate hydrate film growth has been investigated at the hydrocarbon/water interface for cyclopentane and methane hydrate, using video microscopy combined with gas consumption measurements. Hydrate formation was characterized by the film thickness, propagation rate across the hydrocarbon/water interface, and gas consumption. The film formation processes of cyclopentane and methane hydrate were measured over the temperature range of 260-273 K and pressure range of atmospheric to 8.3 MPa. Hydrate formation was initiated by the propagation of a thin, porous film across the hydrocarbon/water interface. This thickening rate was strongly dependent on the hydrate former solubility in the aqueous phase, in the absence and presence of hydrate. The methane hydrate film thickness began at about and grew to a final thickness (20-) which increased with subcooling. The cyclopentane hydrate film thickness began at about and grew to a final thickness (15-) which again increased with subcooling. The hydrate film grew into the water phase. Gas consumption indicated that the aqueous phase supplied hydrate former during the initial hydrate growth, and the free gas supplied the hydrate former for film thickening.     

Inhibitory effects of novel green inhibitors on gas hydrate formation

Natural gas hydrates easily form in pipelines, causing potential safety issues during oil and gas production and transportation. Injecting gas hydrate inhibitors is one of the most effective methods for preventing gas hydrate formation or aggregation. However, some thermodynamic hydrate inhibitors are toxic and harmful to the environment, whereas degradation of kinetic inhibitors is difficult. Therefore, environmentally friendly and easily biodegradable novel green inhibitors have been proposed and investigated. This paper provides a short but systematic review of the inhibitory performance of amino acids, antifreeze proteins, and ionic liquids. For different hydrate formation systems, the influences of the inhibitor type, structure, and concentration on the inhibitory effects are summarized. The mechanism of green inhibitors as kinetic inhibitors is also discussed. The progress described here will facilitate further developments of such green inhibitors for gas hydrate formation.     

水合物浆液流动与流变特性研究进展

水合物浆液技术作为一门新型水合物防治途径和油-气-水多相安全混输的方式逐渐受到油气生产和运输部门的重视。系统综述了国内外水合物浆液流动特征和流变特性的最新研究进展, 主要从研究装置、宏观形态演化、流率/压阻等其他流动参数变化规律及水合物浆液流变性方面进行了详细讨论。介绍了高压流变仪、高压黏度计及水合物流动循环管路等实验装置, 着重分析了水合物循环管路的优缺点;阐述了水相中水合物浆液和油水体系内天然气水合物浆液宏观形态演化的异同;系统研究了水合物形成过程中体系流量/压阻等其他流动参数变化规律;归纳总结了水合物浆液流变性实验和理论模型的研究成果。     

甲烷水合物再汽化分解动力学模型建立

针对水合物法储运气体技术,实验研究了水合物再汽化分解过程,考察了加热温度、初始分解压力和反应器中水合物量等因素对水合物再汽化分解速率的影响。实验结果表明,当反应器中水合物量较多时存在分解速率缓冲现象,减慢了水合物的分解速率,而排气降压可以有效地提高水合物的分解速率。根据实验现象分析了水合物再汽化分解机理,认为水合物的分解速率主要取决于分解推动力的大小,而分解推动力又受传热速率和分解压力等条件的影响。结合传热和水合物分解速率方程,建立了水合物的再汽化分解模型,计算了不同热水温度、不同流量和不同压力等条件下水合物再汽化分解的产气速率,并与实验结果进行了对比,两者总体吻合较好,对存在的误差进行了原因分析。