油气管道水合物生成堵塞机理综述

水合物的生成模型分为热力学和动力学模型,根据管输体系的不同,液相体系和气相体系水合物的形成可分别划为四个阶段。水合物堵塞机理目前比较认可的是聚并机理和管壁沉积理论。以目前研究最为成熟的油基体系水合物生成堵塞为例,介绍堵塞机理并就当前研究现状提出几点展望。     

凹凸棒石体系下CO2水合物生成动力学实验

油气生产、储运及CO₂管道输送的过程中易生成CO₂水合物,添加抑制剂是预防CO₂水合物生成的有效手段。为解决CO₂水合物堵塞问题,本文采用超声波处理后的凹凸棒石作为抑制剂,利用可视化高压反应釜实验装置,在初始条件3 MPa和2℃下,研究了添加浓度为0、0.05mg/mL、0.30mg/mL、0.50mg/mL、0.75mg/mL、1.00mg/mL和1.50 mg/mL的凹凸棒石对CO₂水合物生成动力学的影响。用压力变化法测定了水合物生成诱导时间,用动力学模型计算了水合物生成量,并分析了凹凸棒石影响CO₂水合物生成的微观机理。实验结果表明凹凸棒石能延长CO₂水合物生成诱导时间,浓度为0.75mg/mL时作用效果最佳,较纯水体系CO₂水合物生成诱导时间延长了200%;凹凸棒石能减少CO₂水合物的生成量,浓度为1.5mg/mL时作用效果最佳,与纯水体系相比减少了12.8%。凹凸棒石抑制水合物生成的微观机理主要是由于其独特的选择吸附性以及对传质传热的阻碍。研究表明以凹凸棒石作为CO₂水合物抑制剂效果良好,能有效延长其诱导时间,兼具经济性和环境友好的特点。     

间歇流下二氧化碳水合物生成形态与堵塞机理

为明确二氧化碳水合物在间歇流条件下的生成形态与堵塞机理,采用高压可视实验环路进行了气团流及段塞流体系下的二氧化碳水合物的生成实验,分析了气团流与段塞流下二氧化碳水合物生成及堵塞形态图像。结果表明：气团流下水合物主要生成位置为管道顶部,以持续增长的水合物层的形式逐步减小环路流通面积,最终导致堵塞;段塞流下水合物在液相及管道顶部均有大量生成,但受制于大流量的冲刷,顶部水合物层无法长期存在,破碎落入液相主体中,导致液相主体黏度上升,流动阻力增大,流速下降,进而为液相中絮状水合物的并聚成块提供条件,液相中水合物的不断聚集是段塞流下水合物堵管的主要原因。此外,段塞流下生成的中空水合物球体是一种特殊的水合物形态,这类水合物多形成于液塞区与液膜区交界处。由于其内包裹着气体,故而会浮于液相空间上部,也会受扰动而破碎成片状水合物,但都无法在顶部空间聚集紧实形成致密水合层。     

十六烷基三甲基溴化铵促进CO2水合物生成的实验研究

针对CO2水合物自然生成速度慢这一技术难题,利用实验室自制的水合物实验系统,开展了十六烷基三甲基溴化铵(CTAB)体系下CO2水合物生成促进实验研究。考察了CTAB质量分数为200、300、500、700、900 mg/kg下对水合反应体系表面张力及CO2水合物生成特性影响规律,分析了CTAB对CO2水合物生成促进作用机理。实验结果表明,5种浓度下CTAB添加剂均能够有效降低CO2水合物相平衡点,温度越高,生成压力降低幅度越大,在最优用量为300 mg/kg下降幅可达27.7%。水合反应体系的压力越低,CTAB促进CO2水合物生成的诱导时间降低越大,促进效果越明显。该研究对于提高水合物生成速率具有一定的意义。     

水合物浆在管道中的流动安全

摘要：搭建了环境温度控制室,将直径为42mm,长为30m的不锈钢环道安置在其中。借助于实验环道分别进行了固相体积浓度为0～70％、平均流速为0.5～3.6m.s^-1的四氢呋喃水合物浆和HCFC-141b水合物浆的流动实验。发现管道中两种水合物浆的压降梯度随流速的增加而增加;而与水合物体积浓度的关系都存在一个临界值,分别为50.6％和37.5％,当体积浓度小于临界值时,水合物浆压降梯度随体积浓度的增加而很缓慢的增大;当体积浓度大于临界值时,压降梯度随体积浓度的增加而急剧增大。通过与其他研究的比较,以临界水合物体积浓度为判断标准定义了一个流动安全区,当管道中的水合物体积浓度小于临界值,可以认为是安全的,相反则认为管道存在水合物堵塞的威胁。     

油气管道水合物堵塞机理研究进展

国内外对油气管道水合物堵塞机理的实验研究虽然较多,但一直缺少系统的总结归纳。本文根据水合物堵塞实验开展条件的不同,首先将油气管输体系分为油基体系、水基体系（纯水体系及水主导体系）、气主导体系和部分分散体系。文章分析表明,管道水合物堵塞机理众多,具体包括水合物的聚集和沉积、水合物大量聚集阻塞管道流通截面及油水相分离等。其中,水合物的聚集和沉积是油基体系水合物堵塞的主要机理,水合物颗粒的着床沉积是纯水体系水合物堵塞的主要机理,水合物大量聚集阻塞管道流通截面则是气主导体系水合物堵塞的主要机理。水主导体系和部分分散体系的水合物堵塞机理,目前尚无统一定论,有待进一步深入研究。文章指出对环状流液滴分布、油水分散状态、乳状液稳定性及未乳化自由水层等的量化研究则是未来水合物堵塞机理的研究重点。     

引起管道堵塞的原因分析及对策

简要介绍中海石油化学股份有限公司合成氨装置曾发生过几次因为NH3与CO2反应生成甲铵引起的管道堵塞,对出现的问题进行了分析和探讨,并提出了改造措施。     

粉土中CO2水合物的稳定性条件

测定纯CO₂水合物和干密度为1.40、1.50、1.65 g·cm^-3粉土中CO₂水合物的稳定性条件。通过实验数据的对比分析,表明了粉土孔隙效应对CO₂水合物稳定性条件具有重要影响,较于纯水合物,粉土中水合物稳定性压力更高、温度更低。另外,比较了不同初始分解温度下1.50 g·cm^-3粉土中CO₂水合物的稳定性条件,证明了水合物初始分解温度会对沉积物中水合物的稳定性条件测定产生影响。最后,基于修正的van der Waals-Platteeuw相似文献   

CO2水合物浆在水平圆管中的传热特性

在CO₂水合物浆流动传热特性测试实验系统上,采用套管式电加热的方法对CO₂水合物浆进行了分解实验,并对CO₂水合物浆的流动传热特性进行了分析。对CO₂水合物浆的相变特性进行了研究,得到CO₂水合物浆的相变温度在8～12℃。研究了在固相体积分数为13.2%以及流速为0.45m/s的条件下CO₂水合物浆在内径为8mm的水平不锈钢管中的传热特性,计算得到CO₂水合物浆在不锈钢水平圆管中的对流传热系数为1500～1800 W/(m²·K),并且其在流动传热过程中呈现先增大随后趋向平稳的趋势,在水合物的相变区相应的对流传热系数表现最大。研究了分解加热功率对管壁温和对流传热系数的影响,发现加热功率对管壁温度的影响较强。在实际应用中可利用CO₂水合物浆的相变作用来增强传热,提高传热效率。     

中原油田CO2吞吐试验中近井地带堵塞现象分析

随着CO2吞吐试验的不断扩大,对地层近井地带堵塞现象的认识越来越深刻。针对中原油田CO2单井吞吐试验情况,结合胜利油田及石油大学等关于近井地带发生堵塞现象的室内试验和分析研究成果,认为导致中原油田CO2吞吐试验中近井地带堵塞的原因包括地层水矿化度含量高、无机沉淀物和有机物堵塞的影响,以及生产压差偏大等,为进一步提高CO2吞吐效果提供依据。     

An analysis of liquid CO2 drop formation with and without hydrate formation in static mixers

The formation process of CO₂ drops in various types of Kenics Static Mixers was analyzed from the perspective of energy dissipation in the mixer, focusing on the formation of drop surfaces. Experimental studies on CO₂ drop formation were conducted under varying temperatures, pressure, and flow rates, with and without hydrate formation. Analysis of the CO₂ drop size and distribution at several locations within the static mixer was conducted, as of pressure drop in the mixer, to determine dissipation energies. In all the experimental conditions, by considering the surface energy for hydrate formation, the energy required for the formation of CO₂ drops correlated well with total energy dissipation by mixer flow, which is represented by a pressure drop along the mixer. This process has important applications to the formation of liquid CO₂ for ocean disposal as a countermeasure to global warming. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

海底沉积物层CO2封存中水合物研究进展

海底沉积物层内CO2封存被认为是缓解全球气候变暖的有效途径,本文介绍了CO2封存时水合物自封机理、水合物形成条件和水合物稳定带范围,描述了水合物生成动力学研究现状,包括成核动力学、生长动力学以及水合物结晶过程驱动力,水合物的成核模型有成簇成核模型、成簇成核扩展模型、界面成核模型、Chen-Guo模型,水合物生长动力学模型有Englezos、Kvamme生长模型、指数增长模型、流体流动模型以及LB模型,水合驱动力有化学势差、温差、吉布斯自由能差、浓度差、压差或逸度差。总结了多孔介质渗透率和孔隙度随水合物成核和生长的演化关系,有KC模型、NR模型、平行毛细管束模型、渗透率下降模型和Morisdis相对渗透率模型,最后介绍了CO2水合实验情况,展望了CO2海底沉积物层内封存与水合物相关的科学问题。     

Quantitative analysis of CO2 hydrate formation in porous media by proton NMR

Gas hydrate is a nonstoichiometric crystal compound formed from water and gas. Most nonvisual studies on gas hydrate are unable to detect how much water is converted to hydrates, and thus, the hydrate stoichiometry calculations are inaccurate. This study investigated the CO₂ hydrate formation process in porous media directly and quantitatively. The characteristics of the time-variable consumption of hydrate formation indicated a two-stage formation, hydrate enclathration and continuous occupancy. The enclathration stage occurred in the first 20 min of the formation when considerable heat is released. The continuous occupancy stage lasted longer than the hydrate enclathration because the empty cages in previously formed hydrates would also be occupied. The higher formation pressures can accelerate water consumption and increase cage occupancy. The compositions of completely formed CO₂ hydrates at 2.7, 3.0, and 3.3 MPa and 275.15 K were determined as CO₂·6.90H₂O, CO₂·6.70H₂O, and CO₂·6.49H₂O, respectively.     

初始压力对冰冻石英砂中CO2水合物生成特性的影响

利用冰冻石英砂模拟冻土水合物的赋存条件,研究了压力对二氧化碳水合物生成特性的影响,在300 mL高压水合物反应釜中于271 K下进行了多组CO2液化压力以上及以下的霰状冰粉包裹的石英砂中水合物生成实验。结果表明,充入的CO2未液化时,初始压力越大,水合反应速率越快,压力越早达稳定状态;充入压力达液化压力后,注入的CO2越多,水合反应速率越快。压力作为水合反应的驱动力,压力越高水合物生成越多,冰的最终转化率越高。采用CO2置换冻土区中甲烷水合物时,控制压力低于液化压力或注入过量的CO2,置换效果更好。     

Experimental study of CO2 hydrate formation in porous media with different particle sizes

To investigate the effect of the particle size of porous media on CO₂ hydrate formation, the formation experiments of CO₂ hydrate in porous media with three particle sizes were performed. Three kinds of porous media with mean particle diameters of 2.30 μm (clay level), 5.54 μm (silty sand level), and 229.90 μm (fine sand level) were used in the experiments. In the experiments, the formation temperature range was 277.15–281.15 K and the initial formation pressure range was 3.4–4.8 MPa. The final gas consumption increases with the increase in the initial pressure and the decrease in the formation temperature. The hydrate formation at the initial formation pressure of 4.8 MPa in 229.90 μm porous media is much slower than that at the lower formation pressure and displays multistage. In the experiments with different formation temperatures, the gas consumption rate at the temperature of 279.15 K is the lowest. In 2.30 and 5.54 μm porous media, the hydrate formation rates are similar and faster than those in 229.90 μm porous media. The particle size of the porous media does not affect the final gas consumption. The gas consumption rate per mol of water and the final water conversion increase with the decrease in the water content. The induction time in 5.54 μm porous media is longer than that in 2.30 and 229.90 μm porous media, and the presence of NaCl significantly increases the induction time and decreases the final conversion of water to hydrate.     

Sugar cane juice concentration via CO2 gas hydrate formation

Sugar cane juice concentration via evaporation is the traditional method, though the downside in this technique is the product loss due to sucrose inversion. Gas hydrate separation is an emerging technology applied in desalination, carbon capture, and in this study, for concentrating fruit juice by trapping the water in the form of crystalline cages. A 750 cm³ hydrate reactor was used for hydrate formation experiments to concentrate the sugar cane juice, with a sampling of the concentrate to determine the final solids content. Hydrate formation experiments showed the successful concentration of a 0.12 mass fraction feed to approximately 0.56 mass fraction using four batchwise concentration stages. A comparison of the energy usage between the evaporation train as used in sugar factories and a single batch hydrate formation stage, to concentrate a 0.12 mass fraction feed to 0.30 mass fraction showed an energy reduction of approximately 20% for the hydrate method.     

Investigation of the hydrate formation process in fine sediments by a binary CO2/N2 gas mixture

To obtain the fundamental data of CO₂/N₂ gas mixture hydrate formation kinetics and CO₂ separation and sequestration mechanisms, the gas hydrate formation process by a binary CO₂/N₂ gas mixture (50:50) in fine sediments (150-250 μm) was investigated in a semibatch vessel at variable temperatures(273, 275, and 277 K)and pressures (5.8-7.8 MPa). During the gas hydrate reaction process, the changes in the gaseous phase composition were determined by gas chromatography. The results indicate that the gas hydrate formation process of the binary CO₂/N₂ gas mixture in fine sediments can be reduced to two stages. Firstly, the dissolved gas containing a large amount of CO₂ formed gas hydrates, and then gaseous N₂ participated in the gas hydrate formation. In the second stage, all the dissolved gas was consumed. Thus, both gaseous CO₂ and N₂ diffused into sediment. The first stage in different experiments lasted for 5-15 h, and >60% of the gas was consumed in this period. The gas consumption rate was greater in the first stage than in the second stage. After the completion of gas hydrate formation, the CO₂ content in the gas hydrate was more than that in the gas phase. This indicates that CO₂ formed hydrate easily than N₂ in the binary mixture. Higher operating pressures and lower temperatures increased the gas consumption rate of the binary gas mixture in gas hydrate formation.     

CO2水合分离研究进展

CO2水合分离是一种新型的分离技术。根据CO2排放工艺,CO2水合分离可分为燃后分离和燃前分离。文章论述了CO2水合分离技术的基本原理以及工艺流程与节能降耗等方面的研究进展,指出了CO2水合分离的优缺点,并展望了CO2水合分离技术的研究方向。