表面活性剂对天然气水合物生成促进的研究

天然气水合物又称“可燃冰”，储气能力大，其生成与压力、温度、气水接触面积以及添加剂等因素有关。概述了天然气水合物生成的促进研究现状，介绍了不同类型的表面活性剂，包括阴离子表面活性剂（十二烷基苯磺酸钠SDBS、十二烷基硫酸钠SDS）、非离子表面活性剂（烷基多糖苷APG）对天然气水合物生成的影响，主要研究了不同类型表面活性剂对天然气水合物表观水合数、储气密度以及诱导时间的影响，同时分析了表面活性剂加速天然气水合物生成的机理。结果表明：不同类型的微量表面活性剂都不同程度地促进了天然气水合物的生成，改变了水合物的形成机理；探索研究新的添加剂，有着重大意义。     

表面活性剂对天然气水合物合成影响的实验研究

为研究钻井液化学成分对天然气水合物的影响作用,利用天然气水合物人工合成实验系统进行了天然气水合物的人工合成实验.在天然气水合物的合成过程中,分别对天然气-水溶液体系中加入表面活性剂(Sodium Dodccyl Sulfate)与未加入表面活性剂时水合物的生成时间、生成温度、生成压力及表面活性剂的浓度等对生成过程的影响进行了实验.在加入表面活性剂的天然气-水溶液体系中,由于表面活性剂的存在加速了气体和水溶液体系的接触面,从而加速了水合物的生成、降低了水合物的生成压力、提高了相同条件下的生成温度,即表面活性剂的存在改变了天然气水合物的生成条件,而且增加了水合物中的含气率.因此,表面活性剂用于配置钻井液有利于保持天然气水合物井的井壁稳定.     

表面活性剂对天然气水合物的作用

概述了表面活性剂对天然气水合物的作用, 一方面可用表面活性剂来提高水合物的生成速率, 因天然气水合物的巨大储气特性和方便、安全的存储方式使其具有极大的工业应用前景; 另一方面, 可用表面活性剂来抑制水合物的生成, 在天然气的整个流动过程中, 一旦形成水合物, 就会造成设备及管道堵塞, 影响正常的生产和运输, 甚至造成停产等事故。所以, 加入少量的表面活性剂来避免水合物的生成显得尤为重要。     

喷雾反应器中表面活性剂对制备天然气水合物的影响

天然气水合物作为一种高效、安全的天然气储存和运输的方式,其实用性很大程度上取决于水合物的含气率和气体水合物的生成速率。从理论上分析了在喷雾反应器中表面活性剂的作用机理:表面活性剂的主要作用在于它降低了参与水合物反应的水的表面张力和改变了水合物形态,提高了气体在水中扩散率和传质率,从而加速水合物的生成。实验证明,表面活性剂在降低水溶液表面张力的同时促进了天然气水合物的生成并提高了水合物的储气率。     

低渗透油藏表面活性剂降压增注效果影响因素

表面活性剂通过降低油水界面张力和乳化作用实现低渗透油藏降压增注。通过宏观和微观方法研究界面张力和乳化速率对降压效果的影响,并分析界面张力和乳化速率的协同作用。结果表明,当界面张力小于5.25 mN/m时,能够实现降压作用,且随着界面张力的降低,其降压效果越显著;界面张力下降,采收率上升,但当其降低到10-1mN/m时,表面活性剂提高采收率的增幅有限;界面张力达到10-2 mN/m时,表面活性剂仍无法完全解除水流通道中残余油的附加阻力。当表面活性剂的乳化速率大于0.11 mL/min时,有降压作用,进一步提高乳化速率,从而提高降压率,但当表面活性剂的乳化速率大于0.42 mL/min时,对降压率的影响程度减弱;对采收率增幅的影响为乳化速率加快,采收率增幅加大,当表面活性剂的乳化速率大于0.21 mL/min时,继续增加乳化速率对采收率增幅的影响不大。因此,表面活性剂用于降压增注的表面活性剂形成乳状液的时间短,能够使油水充分乳化,迅速扩大波及面积后再降低界面张力、提高洗油效率,可以更有效地降低驱替压力,提高采收率。     

用动界面张力方法研究原油/盐水界面的性质Ⅰ.原油天然表面活性剂和破乳剂的竞争吸附现象

测定了原油 /盐水的动界面张力 ,比较了在无破乳剂存在时几种体系的动界面张力曲线。证明了原油天然表面活性剂分子渐渐扩散吸附到原油 /盐水界面上 ,当体系中有破乳剂存在时 ,破乳剂分子以竞争的方式扩散吸附到原油 /盐水界面上。用动界面张力方法研究原油天然表面活性剂和破乳剂在原油 /盐水界面的吸附速率对研究原油乳状液的破乳机理和优化破乳条件十分重要。     

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赋存于海底与极地冻土带沉积物孔隙中的天然气水合物，具有能量密度高、分布广泛、规模巨大、埋深较浅、成藏物化条件好等特点，被认为是21世纪潜力巨大的化石燃料的替代资源，引起了世界各国的高度重视。文章综合了各国近年的研究成果，概述了表面活性剂对天然气水合物生成的影响。一方面可以用表面活性剂来抑制油气运输管线中水合物的生成；另一方面也可用它来提高水合物的生成速率，使其在环保、石油天然气、化工、生物等很多领域具有广泛的应用前景。文章最后针对我国目前的情况，提出了今后研究工作的发展方向。     

含烷氧基链节的硫酸盐表面活性剂的油-水界面张力及其对原油的乳化能力

 以壬基酚、十二醇、异构十三醇为主要原料，合成了7种含烷氧基链节的硫酸盐表面活性剂。测定了以含0.1%(质量分数) 硫酸盐表面活性剂的模拟盐水与桩106-15-X18普通稠油配制的油-水体系的界面张力，并测定了上述表面活性剂对桩106-15-X18普通稠油的乳化速率。结果表明，虽然这些表面活性剂具有较高的耐盐能力，但随着分子中氧丙烯链节数逐渐增加，油-水界面张力值最小时对应的最佳NaCl含量呈降低趋势。在合成含烷氧基链节的硫酸盐表面活性剂时，可以通过控制氧丙烯链节长度，调节其在油-水体系中获得的低界面张力区的特点，使之适应不同盐含量的地层。含烷氧基链节的硫酸盐表面活性剂降低油-水界面张力的能力和其对稠油的乳化速率没有简单的对应关系。     

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天然气水合物是一种类似冰的笼型晶体水合物。它的生成与压力，温度，气水接触面积以及添加剂等因素有关。利用天然气水合物储气实验台，实验研究了不同类型的表面活性剂（包括阴离子表面活性剂，非离子表面活性剂）对天然气水合物生成的影响，主要研究了它们对天然气水合物生成速度，储气密度，诱导时间以及虚拟水合数的影响。结果表明：不同类型的表面活性都不同程度提高了水合物生长速度和储气密度，缩短了水合物形成的诱导时间，并使虚拟水合数接近于理论值。     

天然气水合物储气量及分解安全性研究

利用可视化实验设备，研究了表面活性剂T40、T80及其复配溶液构成的5组反应体系中Ⅱ型气体水合物的储气及其分解情况，利用定温压力搜索法测定了水合物分解热平衡条件，并运用含气率、分解速度及分解热理论对实验数据进行了计算。结果表明，合成的天然气水合物样品含气率高、分解速度小。从传质和传热两方面分别分析了表面活性剂和水合物分解热对实验体系中气体-溶液-天然气水合物三者界面之间物质和热量传递过程的影响；分析结果表明：适当表面活性剂的加入有利于提高天然气水合物的储气量，水合物的高分解热是其分解速度低的主要原因。水合物的高储气性和分解安全性为天然气水合物储运技术的实践奠定了基础。     

添加剂对CO2水合物生成的影响

以水合物的方式分离/储存CO₂气体是一项具有挑战性的新技术。为了提高水合物的生成速率和储气密度，在小型可视化的水合物反应装置上实验研究了不同种类的添加剂对CO₂水合物生成特性的影响。结果表明，实验用有机硅系列添加剂可以有效降低气-水界面的表面张力，提高水合物的生成速率。CO₂水合物的生成量随着添加剂浓度的增大而增大，但当浓度高于0.1%以后，其生成量增长非常缓慢。单组分添加剂Silwet L-77效果最好，而单组分添加剂THF对CO₂水合物的生成没有任何改善，但将浓度为4%的THF和1%的Silwet L-77混合后却对水合物的生成起到了显著的改善效果，12 h内的气体压降可达到0.27 MPa，是纯水体系的10倍之多，照片显示有大量的水合物生成。研究结果对寻找适合于CO₂水合物快速生成的添加剂，为其应用于高效分离储存CO₂气体技术等方面提供了指导。     

Natural gas hydrate formation dynamics in a diesel water-in-oil emulsion system

Abstract

Although gas hydrate is an excellent clean fuel and energy storage form, its natural generation rate is very slow. The key to accelerate the industrialization is to find an appropriate promotion method. In this paper, Span80 and Tween80 were used to study the rapid formation technology of hydrate in diesel water-in-oil emulsion at 275.15 K and 7?MPa. Firstly, hydrate formation in different water cut systems was studied. Results show that hydrate with higher water cut has a faster formation rate and a higher gas storage density, and the system has the shortest induction time with a 40% water cut. The addition of PEG400 and SDS to the original emulsion system resulted in higher gas densities and denser hydrates. Moreover, the addition of emulsifier can reduce the interfacial energy and form a stable interface membrane. Gas storage density also reflects the same phenomenon. Finally, the double electron layer structure formed by different charged ions can also make the emulsion system more stable and promote hydrate formation. Hydrate can be rapidly formed in the diesel water-in-oil emulsion system, which has a great reference value for the future hydrate storage and transportation.     

Effect of a nonionic surfactant on the formation of natural gas hydrate in a diesel emulsion system

Abstract

In order to investigate the effect of different nonionic surfactants on hydrate formation in oil-water emulsion systems, the hydrate formation experiments were carried out in a diesel water-in-oil emulsion system with a water cut of 40% using nonionic surfactants such as Span80, Tween80, Span20 and Tween20, respectively. The results show that under the experimental conditions of 275?K and 7?MPa, a certain concentration of nonionic surfactant can promote the growth of hydrates in diesel emulsion systems, shorten the hydration reaction time, and have a significant effect on the improvement of gas storage density. The combination of Span80 and Tween80 in a mass ratio of 1:1 was the most effective in promoting the formation of hydrate in the emulsion system. When the mass fraction was 0.5%, the hydration reaction time was the shortest and the hydrate gas storage density was the highest. Due to the addition of the nonionic surfactant, a stable interfacial film and interfacial charge are formed around the water droplets of the emulsion system, making it difficult for the droplets to approach and polymerize, which maintains the stability of the water-in-oil emulsion system and has great reference value for the study of hydrate storage and transportation.     

Rate of hydrate formation in crude oil/gas/water emulsions with different water cuts

The formation of gas hydrates in gas and oil subsea pipelines can result in blockages and shutdowns. Understanding of the formation process and its kinetics will be helpful for predictions of the amount of hydrates expected to form under defined conditions. In the present work, mixed gas hydrates of methane, ethane and propane are formed in crude oil emulsions with different water cuts in a stirred constant volume high pressure cell. The rate of hydrate formation for each crude oil is evaluated at different stirring rates. The stability of the emulsion made by each crude oil is also tested at different water cuts and stirring rates. At 80% water cut, hydrate growth occurs in two steps. The first step displays slow growth. The transition between the steps corresponds with inversion of the emulsion. Regarding the stability of emulsion, more stable emulsions are correlated to higher rates of hydrate formation. The rate of hydrate formation at 50% water cut was higher than at 80% water cut independent of oil composition and stirring rate.     

盐含量对天然气水合物防聚剂性能的影响

传统的天然气水合物(以下简称水合物)防聚剂评价实验一般在纯水中进行,而现场的水相中通常会混入一定的海水或含有矿化度的地下水,因而前者的评价结果与现场的实际情况存在着较大的差距。为了在更加接近现场实际情况的条件下评价水合物防聚剂的性能,首先使用高压透明蓝宝石釜从宏观角度对水合物浆液的形态进行观察,然后应用粒度仪从微米级进行水合物浆液中液滴—水合物粒径分布的观察测试,最后结合油水界面张力的变化规律对含盐体系水合物防聚剂的防聚行能进行了分析。研究结果表明:①在含3%NaCl条件下,水合物防聚剂CJ(以下简称CJ)对水合物的防聚效果较好;②水合物形成以前,在机械力的搅拌作用下,含CJ的水合物乳液粒径随着含盐量的增加而减小,含盐有利于液滴在油相中的分布;③水合物形成以后,在含3%NaCl的条件下,水合物颗粒分布更小,适量的盐有利于水合物形态的控制;④在2℃条件下,含盐量为3%时,油水界面张力值为最大,达到4.453 mN/m。结论认为,随着盐含量的增加,CJ对水合物的抑制效果增强,但在水合物形成以后抑制效果则不明显,相反盐含量的增加还容易破坏油水乳液的稳定性甚至破坏水合物防聚剂的使用效果。     

天然气水合物生成的影响因素及敏感性分析

天然气水合物是由某些气体或它们的混合物与水在一定温度、压力条件下生成的一种冰状笼型化合物。进行水合物生成条件的敏感性研究对预防天然气水合物的生成有着重要意义。分析了温度、压力两个主导因素的影响,提出了临界温度的概念;验证了盐类对水合物生成的抑制作用;剖析了天然气各组分对水合物生成的敏感程度。得出:水合物生成温度随着压力的增加而升高,但是存在一个临界温度,当环境温度达到该值时,压力对水合物生成的影响很小;甲烷虽然是生成水合物的主要组分,但当其含量趋近100%时,却不易形成水合物;乙烷不是敏感组分;丙烷对水合物生成的影响较乙烷大;异丁烷这类重烃组分,由于其分子大小和Ⅱ型结构中的大洞穴尺寸相匹配,所以对Ⅱ型结构的稳定能力远大于其它分子,当其含量较小时,就易生成Ⅱ型结构水合物;CO2和HS这类酸性气体,易溶水从而能促进水合物的生成。     

PROBABLE GAS HYDRATE IN CONTINENTAL SLOPE EAST OF THE NORTH ISLAND, NEW ZEALAND

Anomolous seismic horizons which (1) are strongly reflective, i.e. have a high impedence contrast; (2)cut across bedding planes of sediments;(3)are subparallel with the sea floor; and (4)increase their sub-bottom depth with increasing depth of sea floor (and thus with decreasing temperature of bottom water) are tentavely identifed as the base of a gas hydrate layer. The anamalous reflections occur below waters 1000-2500m deep, and along 500km of the continental slope. Some 10–20,000 sq km appear to be underlain by gas hydrates.
The hydrate layer is often associated with structural anomalies(anticlines, tilted faultblocks). These would allow gas to migrate up-dip into pressure and temperature conditions suitable for hydrate formation. Since the hydrate-cemented layer itself acts as a barrier to gas migration, free gas will be trapped and accumulated in the sediments beneath it.
It is concluded that huge amounts of hydrocarbon gas, both free gas and solid hydrate, have accumulated in this continental margin. On land, gas and oil generation is widespread, mainly originating from overpressured, Lower Teritiary to Upper Cretaceous shales. From seismic evidence the same formations appear to extend under the shelf and continental slope. The extensive occurence of gas hydrates would confirm that organicrich, terrigenous sediments have extensively been deposited in these areas.     

甲烷水合物在煤层中存在的可能性

已有实验证明：在一定的温度下，只要压力合适，有甲烷气源和水，就能合成甲烷水合物，而且多孔介质的存在将有助于水合物的形成。煤是一种多孔介质，在其形成过程中生成了大量的甲烷，并含有大量的水份。受构造应力和地应力的影响，煤层中存在着褶皱、断层等，结构复杂，因而在煤层中存在高应力区，而这种高应力区为甲烷水合物的存在创造了条件，同时，在一些煤与瓦斯突出中，吨煤瓦斯突出量高出吨煤瓦斯含量很多，以致无法解释，更为煤层中的局部地点存在甲烷水合物提供了佐证。因此，推断煤层中可能存在零散分布的甲烷水合物。     

Analysis of natural gas hydrate formation in sodium dodecyl sulfate and quartz sand complex system under saline environment

Under natural conditions, natural gas hydrate occurs in the pores of porous media found in the sedimentary layer. Thus, the rapid formation and basic properties of the hydrate in the porous medium must be studied. Quartz sand with different particle sizes compounded with Sodium Dodecyl Sulfate solution was used to study the hydrate formation in the system at 275.15 K and 6 MPa under a saline environment. Results were as follows. 1) Methane gas uptake in a saline system with NaCl concentration of 50 mmol was higher than that in pure water. This finding indicated that although the salt is a thermodynamic inhibitor, low concentration of NaCl can promote the formation of hydrates. 2) In the initial stage of the experiment, the rate of hydrate formation in saline environment was significantly higher than that in pure water. After approximately 1 h, the formation rate of hydrate in the compound system decreased under a saltwater environment and was lower than that in the complex system under pure water. 3) The hydrogen bond network inside the high-concentration NaCl solution was seriously damaged. In this case, water molecules cannot easily form a cage structure, and the presence of chlorine ions weakens the stability of a small amount of formed hydrate cage, thereby further inhibiting the formation of hydrates. However, in the low-concentration NaCl system, mass transfer is improved, and the formation of hydrate is promoted because of the weakened hydrogen bonding at the gas–liquid interface.