气液比对表面活性剂复配促进甲烷水合物生成影响

气液比作为影响天然气水合物快速、大量生成的关键因素,有必要对其深入研究.利用天然气水合物装置,设定初始压力为6 MPa,温度为275.15 K,研究了十二烷基硫酸钠(SDS)与烷基多糖苷(APG1214)复配溶液体系在不同气液比条件下对天然气水合物生成影响.结果表明,合理的选取气液比能增强水合物的储气能力以及生成速率,...     

表面活性剂的酸碱度对甲烷水合物生成的影响

针对甲烷水合物的快速制备,在初始压力7MPa和恒温2℃条件下采用脂肪醇聚氧乙烯醚硫酸钠(AES)阴离子表面活性剂和烷基多糖苷(APG1214)非离子表面活性,通过改变表面活性剂溶液的酸碱性,观察不同pH值对水合物的促进能力,并以表面活性剂分子吸附理论为基础进行分析。结果表明,在pH=3强酸条件下,水合物在气-液界面处先形成晶核,阻碍了气液继续接触,储气密度最低;在pH=11强碱性条件下,晶核在固-液界面处成核,水合物生成速率最高,储气密度最大。     

表面活性剂吸附对促进甲烷水合物生成效果的影响

基于表面活性剂固-液界面吸附理论,在无搅拌条件下研究了十二烷基硫酸钠（SDS（、脂肪醇聚乙烯醚硫酸钠（AES（、脂肪醇聚乙烯醚（AEO（3种表面活性剂在不锈钢反应釜中对甲烷水合物生成的促进效果。结果表明：水合物的生成形态与表面活性剂吸附金属表面形态有良好的对应关系;SDS与AES在金属表面的吸附作用可使水合物成核速率提高,成核位置增多。由于AEO不能在金属壁面发生吸附,导致对水合物生成促进效果降低,在浓度为300 mg·L^-1的SDS、AES和AEO溶液中,水合物储气密度及平均储气速率分别为131.4、128.3、12.3（体积比（和5.8、7.6、0.07 mmol·min^-1;逐步提高SDS溶液浓度（80~1200 mg·L^-1（和AES溶液浓度（60~1350 mg·L^-1（,水合物储气密度首先增大然后减小,储气速率线性增大。因此,合理选择表面活性剂种类及浓度,可显著促进水合物生成。     

SDS与AEP的复配体系下天然气水合物生成分析

在天然气水合物储运技术的运用中,添加表面活性剂是一种被广泛应用的高效促进水合物形成的方法,其中表面活性剂的复配体系对天然气水合物生成的促进影响也是一个重要的研究方向。针对天然气水合物的大量快速制备,在初始压力7 MPa和2℃恒温条件下采用不同质量浓度的十二烷基硫酸钠（SDS）和脂肪醇聚氧乙烯醚磷酸酯（AEP）进行复配,观察不同质量浓度的复配体系对天然气水合物生成速率以及吸气量的影响。结果表明：在AEP溶液中,最终吸气量随着溶液质量浓度的增加而增加;但是由于壁垒效应的存在,阻碍了气体进一步溶解进入溶液中,延缓了水合物的生成,使得AEP溶液中水合物的生长速率与最终吸气量要低于SDS溶液;在SDS与AEP共同作用下,复配体系下水合物的生成速率与吸气量要大于单一体系下水合物的生成速率与吸气量。     

表面活性剂对气液传质的影响

引言在气液相际传质的研究中,有许多有关表面活性剂能降低传质膜系数的报道．Davies在其《湍动现象》一书中做了较为详细的讨论,Davies认为,少量的表面活性剂使界面产生一层附加的薄膜,这层薄膜产生的应力将阻碍表面运动．实际上,气液相际传质通常总是伴有或强或弱的界面湍动,表面活性剂不仅改变界面湍动状况,而且对近界面浓度也有较大的影响．本文利用显微激光全息干涉技术对比进行了研究．1实验1.1装置液体折射率与密度有关,只要测出物场中的折射率变化,就可得到其浓度场的信息．利用激光全息干涉技术不仅可以测定浓度场的变化…     

表面活性剂及其复配体系

本文主要介绍了表面活性的种类、特性以及复配方法。并着重介绍了复配体系的复配方法、性能以及应用用于学习交流。     

表面活性剂对甲烷水合物生成影响研究进展

由于甲烷水合物在自然条件下的生成存在着诱导期时间过长,晶体生长速率过慢等问题,导致其工业化制备受阻,在分析了众多促进水合物生成的研究后,综述了表面活性剂作为高效促生成化学试剂,其复配使用和与多孔介质的协同作用对甲烷水合物生成的影响,并分析了胶束的产生对甲烷水合物生成的促进因素,完整地归纳了表面活性剂溶液中水合物生成的动...     

表面活性剂对甲烷水合物生成影响研究进展

由于甲烷水合物在自然条件下的生成存在着诱导期时间过长,晶体生长速率过慢等问题,导致其工业化制备受阻,在分析了众多促进水合物生成的研究后,综述了表面活性剂作为高效促生成化学试剂,其复配使用和与多孔介质的协同作用对甲烷水合物生成的影响,并分析了胶束的产生对甲烷水合物生成的促进因素,完整地归纳了表面活性剂溶液中水合物生成的动力学模型。最后提出,表面活性剂分子的结构性质与其在溶液中发生的复杂电化学行为对甲烷水合物生成的影响还需进一步的证明与探讨;表面活性剂分子间的相互作用是否存在着提高表面活性剂活性强度仍需作进一步研究。     

表面活性剂的复配

从理论上解释通过表面活性剂的复配，使乳液稳定性提高的原因。     

SDS对甲烷水合物生成动力学和微观结构的影响

表面活性剂是促进水合物生成的有效手段之一。在高压反应釜中研究了十二烷基硫酸钠（SDS）对水合物生成过程的动力学影响,利用XRD和拉曼光谱探究了SDS存在条件下水合物的微观结构。宏观结果表明SDS缩短了诱导时间,加快了水合物生长速率。微观结果表明SDS没有影响sI型水合物的晶型结构,晶面间距与理想sI型水合物及纯水甲烷对比误差在千分之几。水合物中甲烷在大笼小笼中的拉曼位移分别为2904和2915 cm^-1,SDS没有改变大笼小笼结构。大笼绝对占有率（q_L）接近饱和时,SDS可以进一步提高小笼绝对占有率（q_S）,从微观角度证明了SDS可以减少水合数,提高储气率。     

Effect of different surfactants on methane hydrate formation rate, stability and storage capacity

The effects of anionic surfactants sodium dodecyl sulfate (SDS) and linear alkyl benzene sulfonate (LABS), cationic surfactant cetyl trimethyl ammonium bromide (CTAB) and non-ionic surfactant ethoxylated nonylphenol (ENP) on the formation, dissociation and storage capacity of methane hydrate have been investigated. Each surfactant was tested with 3 concentrations 300, 500 and 1000 ppm and it has been found that SDS, when prepared with these three concentrations speeds up the hydrate formation rate effectively. LABS increases the hydrate formation rate at 500 and 1000 ppm but decreases it at 300 ppm. CTAB and ENP have promotion effect on hydrate formation rate at 1000 ppm but decrease it at 300 and 500 ppm. Hydrate stability tests have been performed at three temperatures 268.2, 270.2 and 272.2 K with and without surfactant promoters. The results show that all tested additives increase the dissociation rate of methane hydrate below the ice point. CTAB has the minimum and LABS the maximum effect on the methane hydrate dissociation rate. Experimental results on hydrate gas content revealed that maximum storage capacity of 165 V/V is obtained with 1000 ppm of CTAB in water.     

卵磷脂对甲烷水合物形成的影响

建立了用于测定卵磷脂(lecithin)对钻井液中水合物形成影响的实验装置及方法,以理解化学添加剂卵磷脂对北极Cascade地区钻井过程中水合物层的稳定作用。本研究旨在理解卵磷脂对纯水中甲烷水合物形成热力学和动力学的影响。结果表明,卵磷脂基本上不影响甲烷水合物生成的热力学条件,但当卵磷脂在水中的浓度超过0.003 g·g^-1时,它会影响甲烷水合物的生成速度和数量,是很好的水合物生成动力学促进剂。     

Effect of multi-walled carbon nanotubes on methane hydrate formation

1 m³ of methane hydrate can be decomposed into a maximum of 216 m³ of methane gas under standard conditions. If these characteristics of hydrates are utilized in the opposite sense, natural gas can be fixed into water in the form of a hydrate solid. Therefore, the use of hydrates is considered to be a great way to transport and store natural gas in large quantities. However, when methane hydrate is formed artificially, the amount of gas that is consumed is relatively low, due to the slow reaction rate between water and methane gas. Therefore, for practical purposes in the application, the present investigation focuses on increasing the rate of formation of the hydrate and the amount of gas consumed by adding multi-walled carbon nanotubes (MWCNTs) to pure water. The results show that when 0.004 wt% of multi-walled carbon nanotubes was added to pure water, the amount of gas consumed was about 300% higher than that in pure water and the hydrate formation time decreased at a low subcooling temperature.     

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.     

甲烷水合物生成分解的实验研究

海底存在着大量可燃冰,1 m3可燃冰能够储存160 m3的天然气。因此,可燃冰的开采与利用可燃冰储存与运输天然气具有重要意义。在改变搅拌、过冷度及低浓度动力学抑制剂的条件下,对甲烷水合物生成量与生成速率进行了实验研究。将甲烷水合物进行升温分解,分析水合物分解时的压力变化情况。结果表明:搅拌对甲烷水合物生成的促进效果最好,其次是过冷度,最后是超低浓度动力学抑制剂;水合物生成的传质过程最终被阻碍,采取将水与天然气的上下位置交换的方法,可以生成更多水合物。水合物升温可以得到相平衡曲线;改变初始时刻压力,可以得到不同温度区间的相平衡曲线;降低水合物分解时的升温速度,可以得到更长温度区间的相平衡曲线。     

Study on methane hydrate formation using ultrasonic waves

Methane hydrate is a kind of gas hydrate and has the crystal structure I. 1 m³ of methane hydrate can be decomposed to a maximum of 172 m³ of methane gas in standard conditions. If this characteristic of methane hydrate is reversely utilized, natural gas, which mainly consists of methane gas, is fixed into water in the form of hydrate solid. However, when methane hydrate is formed artificially by simply reversing its process of natural generation, the amount of methane gas consumed owing to hydrate formation is fairly low, which would be problematic for its massive synthesis and application. In this study, experiments are carried out with the goal of increasing the amount of gas consumed by using ultrasonic waves. The power for maximum gas consumption was observed at 150 W, and the amount of gas consumed was four times higher than that at 0 W at the subcooling temperature of 0.5 K. The ultrasonic waves are more effective at the subcooling temperature of 5.7 K than at the subcooling temperature of 0.5 K, and are another effective method for enhancing methane hydrate formation and reducing the hydrate formation time.     

Effect of surfactant on the formation and dissociation kinetic behavior of methane hydrate

The effects of anionic surfactant sodium dodecyl sulfate (SDS) on the formation/dissociation kinetic behaviors of methane hydrate have been studied experimentally, with an emphasis put on dissociation kinetic behavior below ice point. The experimental results on hydrate formation show that the formation rates of methane hydrate could be speeded up by adding SDS to water and a critical SDS concentration of 650 ppm corresponding to a maximum storage capacity of 170V/V is determined. The SDS concentrations are fixed at this value in preparing hydrate samples for all dissociation tests. The dissociation experiments have been performed in two ways, at atmospheric pressure where the dissociation rates are determined by measuring the accumulative evolved gas volume, and in a closed system where the dissociation rates are determined by measuring the increasing system pressure profiles. For comparison, the dissociation tests with respect to two different cases, with and without the presence of SDS, are done in parallel. The results from tests in the first way show that the presence of SDS increases the dissociation rate of methane hydrate in whole temperature region below ice point. The results for the second way are somewhat different. The presence of SDS increases the dissociation rate and meta-stable system pressure in temperature region lower than . But when temperature is equal to or higher than , SDS speeds up the dissociation process only in beginning period, it turns to suppress the dissociation of methane hydrate several hours later and leads to a lower meta-stable system pressure compared with the case of without SDS. The experiments in closed system also demonstrate that the dissociating system approaches a meta-stable state with a pressure much lower than equilibrium dissociation pressure.     

A kinetic study of methane hydrate formation

The kinetics of methane hydrate formation, after commencement of nucleation, were studied using a semibatch stirred tank reactor. The temperatures studied in the experiments were from 274 to 284 K over a pressure range of 3–10 MPa. The results of the experiments revealed that the formation kinetics were dependent on the interfacial area, pressure, temperature and degree of supercooling. The history of water sample affected the induction delay times for nuclei formation, but it had no observable effects on the overall kinetics of hydrate formation after the nucleation had commenced. A consistent semi-empirical model was formulated to correlate the experimental kinetic data.     

煤层气水合物定容生成实验研究

为了有效利用与回收直接排放的大量抽放瓦斯,提出了利用水合物技术处理与储运的新方法,根据气体成分确立了水合物生成的温度与压力条件,通过对气体进行初始压力为9.5 MPa的定容法实验,研究了含表面活性剂下水合物生成过程中温度-压力与CH4转化率的变化规律。实验结果表明,水合反应的进行应保持一定的反应驱动力,根据不同温度下反应驱动力进而确定最佳反应条件,同时反应过程中CH4能被有效提取,但要进行高效生产,应进行多级水合分离技术以提高产率。     

石英砂粒径大小对甲烷水合物形成及分布的影响

为了研究不同粒径多孔介质体系中甲烷水合物的形成,本文采用粒径分别为0.075~0.5mm、0.5~1mm、1~2mm和2~3mm的石英砂作为多孔介质,在初始压力7.0MPa、温度0.5℃条件下进行水合物形成实验并进行取样观察、分层分解,得出不同粒径大小石英砂中甲烷水合物形成及分布的特征。结果表明：随着石英砂粒径的增大,石英砂砂体中的水合物形成量和初始水合物形成速率在逐渐减小;在粒径为0.075~0.5mm、1~2mm和2~3mm石英砂中,充气过程中水合物便开始形成,且并未出现明显的水合物大量形成阶段,而在粒径为0.5~1mm石英砂体系中出现了水合物大量形成的阶段;通过计算发现,0.5~1mm石英砂体系的气体消耗量最大,为0.47mol,2~3mm石英砂体系的气体消耗量最小,仅为0.05mol;在这4种粒径的石英砂体表面的甲烷水合物主要以分散状均匀分布于颗粒之间或胶结成块,但这一观察结果与通过分解的方法所得到的石英砂上部水合物形成量大于下部的结果存在差异;重复实验也发现,仅在粒径为0.5~1mm石英砂顶部出现了水合物大量富集的现象,因此推断认为在一定粒径的介质体系同时上部存在较大空隙时,水合物有可能会在空隙中大量富集存在。这一实验结果对自然环境中水合物的赋存区域及形态的预测具有一定的参考价值。