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.     

Computational modeling of methane hydrate dissociation in a sandstone core

Hydrate dissociation in a porous sandstone core was studied using a computer modeling approach. It was assumed that the hydrate was dispersed in the pores of the core. Using FLUENT^TM code, an axisymmetric model of the core was developed and solved for multiphase flows during the hydrate dissociation. The core model contained three separate phases: methane hydrate, methane gas, and liquid water. At the start of simulation, the valve at one end of the core was opened exposing the core to low pressure; hydrate began to dissociate and methane gas and water began to flow. The depressurization was controlled by adjusting the pressure of the outlet valve.A comprehensive Users’ Defined Subroutine (UDS) for analysis of hydrate dissociation process into the FLUENT code was developed. The new UDS uses the kinetic model introduced by Kim et al. [Kim. H.C., Bishnoi, P.R., Heidemann, R.A., Rizvi, S.S.H., 1987. Kinetics of methane hydrate decomposition. Chemical Engineering Science 42, 1645-1653.] and can model multiple zones dissociation and multiphase flows. Variations of relative permeability of the core were included using Corey's model. The new model allows for variation of the porosity with hydrate saturation.For different core temperatures and various outlet valve pressures, the spatial and temporal variations of temperature, pressure, and flow fields in the core were simulated. The time evolutions of methane gas and water flow rate at the outlet were also evaluated. It was shown that the rate of hydrate dissociation in a core was a sensitive function of surrounding environment temperature, outlet pressure condition, and permeability.     

Methane hydrate formation and dissociation behaviors in montmorillonite

The methane hydrate formation and the methane hydrate dissociation behaviors in montmorillonite are experimentally studied. Through the analyses of the microstructure characteristic, the study obtains the porous characteristic of montmorillonite. It is indicated that methane hydrate in montmorillonite forms the structure I(sI) crystal.Meanwhile, molecular dynamics simulation is carried out to study the processes of the methane hydrate formation and the methane hydrate dissociation in montmorillonite. The microstructure and microscopic properties are analyzed. The methane hydrate formation and methane hydrate dissociation mechanisms in the montmorillonite nanopore and on the montmorillonite surface are expounded. Combining the experimental and simulating analyses,the results indicate the methane hydrate formation and methane hydrate dissociation processes have little influence upon the crystal structure of porous media from either micro-or macro-analysis. It is beneficial to the fundamental researches on the exploitation and security control technologies of natural gas hydrate in deep-sea sediments.     

Methane hydrates bearing synthetic sediments—Experimental and numerical approaches of the dissociation

The production of methane gas from methane hydrate bearing sediments may reach an industrial scale in the next decades owing to the huge energy reserve it represents.However the dissociation of methane hydrate in a porous medium is still poorly understood and controlled: the melting of methane hydrate involves fluids flows and heat transfer through a porous medium whose properties evolve as the hydrate phase disappears, and is replaced (or not) by an ice phase. Mass and heat transfers can be coupled in a complex way, firstly because of the permeability changes, and secondly due to material conduction changes. In our work, mass and heat transfers have been studied both experimentally and numerically.A 2D numerical model is proposed where heat and mass transfers govern the dissociation of methane hydrate. This model has been used to design an experimental device. Experiments have been obtained and finally the model has been validated.The experimental set-up consists of five cylindrical sand packs having the same diameter but different lengths. Each experiment starts by crystallizing a hydrate phase in a porous medium. Then the hydrate is dissociated by controlling the pressure at one boundary. The kinetic of dissociation is monitored by collecting gases in ballast. Simulations and experiments demonstrate that the dissociation limiting step switches from thermal transfer to mass transfer depending on the initial permeability and conductivity of the porous medium.     

泡沫铜强化甲烷水合物生成动力学实验研究

提高水合物生成速率和储气密度对天然气水合物技术应用非常重要。将三种孔密度的泡沫铜（CF）分别浸入十二烷基硫酸钠（SDS）溶液中构建水合储气强化体系,在高压静态反应釜中研究泡沫金属对甲烷水合物生成动力学特性。实验结果表明,泡沫铜骨架能为水合物生成提供充足的结晶点,同时可作为水合物生长过程水合热迁移的“高速公路”。甲烷水合物在SDS/CF体系中可快速生成,最大水合储气速率分布在19.24~21.04 mmol·mol^-1·min^-1之间,其中添加15 PPI泡沫铜的SDS溶液储气量最高（139 mmol·mol^-1）,且达到最大储气量90%所用时间最短（10.1 min）。在6.0~8.0 MPa压力下,相比SDS溶液,添加15 PPI泡沫铜的SDS溶液储气量提高了8.8%~35.6%,储气速率提高了4.7%~40.4%;特别在压力为5.0 MPa时,该孔密度SDS/CF体系储气量甚至比SDS溶液增加13倍,储气速率增加16倍。     

Kinetic simulation of methane hydrate formation and dissociation in porous media

The vast amount of hydrocarbon gas deposited in the earth's crust as gas hydrates has significant implications for future energy supply and global climate. A 3-D simulator for methane hydrate formation and dissociation in porous media is developed for designing and interpreting laboratory and field hydrate experiments. Four components (hydrate, methane, water and salt) and five phases (hydrate, gas, aqueous-phase, ice and salt precipitate) are considered in the simulator. The intrinsic kinetics of hydrate formation or dissociation is considered using the Kim-Bishnoi model. Water freezing and ice melting are tracked with primary variable switch method (PVSM) by assuming equilibrium phase transition. Mass transport, including two-phase flow and molecular diffusions, and heat transfer involved in formation or dissociation of hydrates are included in the governing equations, which are discretized with finite volume difference method and are solved in a fully implicit manner. The developed simulator is used here to study the formation and the dissociation of hydrates in laboratory-scale core samples. In hydrate formation from the system of gas and ice (G+I) and in hydrate dissociation systems where ice appears, the equilibrium between aqueous-phase and ice (A-I) is found to have a “blocking” effect on heat transfer when salt is absent from the system. Increase of initial temperature (at constant outlet pressure), introduction of salt component into the system, decrease of outlet pressure, and increase of boundary heat transfer coefficient can lead to faster hydrate dissociation.     

甲烷-四氢呋喃-水体系水合物生成动力学的实验和模型化研究

研究了透明鼓泡塔中含促进剂四氢呋喃（THF）体系中甲烷水合物的生成动力学.分别考察了进气速率、温度、压力、水合物体积分数对甲烷消耗速率的影响.根据Chen-Guo水合物生成机理,采用基础水合物生成反应的量纲1 Gibbs自由焓变-ΔG/RT作为反应的推动力,建立了水合物生成动力学模型,模型中考虑了体系温度、压力和气液接触比表面积的影响.把模型应用于甲烷气体消耗速率的计算,其模型预算结果与实验数据吻合良好,实验结果和反应动力学模型将有助于工业水合反应器的设计和操作条件的设定.     

Reaction rate constant of methane clathrate formation

Particle size distribution measurements were performed during the growth stage of methane hydrate formation in a semi-batch stirred tank crystallizer. Experiments were carried out at temperatures between 275.1 and 279.2 K and pressures ranging from 3873 to 5593 kPa. The reaction rate constant of methane hydrate formation was determined using the model of Bergeron and Servio (AIChE J 2008;54:2964). The experimental reaction rate constant was found to increase with temperature, following an Arrhenius-type relationship, from 8.3 × 10⁻⁸ m/s to 6.15 × 10⁻⁷ m/s over the 4° range investigated, resulting in an activation energy of 323 kJ/mol. An increase in pressure of approximately 600 kPa did not have any effect on the reaction rate constant. Population balances, based on the measured critical nuclei diameter and that predicted by homogeneous nucleation theory, were also used for comparison purposes. The initial number of hydrate particles was calculated using the mole fraction of methane in the bulk liquid phase and compared to that predicted by an energy balance.     

Dissociation characteristics of methane hydrate using depressurization combined with thermal stimulation

Methane hydrate is considered as a potential energy source in the future due to its abundant reserves and high energy density. To investigate the influence of initial hydrate saturation, production pressure, and the temperature of thermal stimulation on gas production rate and cumulative gas production percentage, we conducted the methane hydrate dissociation experiments using depressurization, thermal stimulation and a combination of two methods in this study. It is found that when the gas production pressures are the same, the higher the hydrate initial saturation, the greater change in hydrate reservoir temperature. Therefore, it is easier to appear the phenomenon of icing and hydrate reformation when the hydrate saturation is higher. For example, the reservoir temperature dropped to below zero in depressurization process when the hydrate saturation was about 37%. However, the same phenomenon didn't appear as the saturation was about 12%. This may be due to more free gas in the reservoir with hydrate saturated of 37%. We also find that the temperature variation of reservoir can be reduced effectively by combination of depressurization and thermal stimulation method. And the average gas production rate is highest with combined method in the experiments. When the pressure of gas production is 2 MPa, compared with depressurization, the average of gas production can increase 54% when the combined method is used. The efficiency of gas production is very low when thermal stimulation was used alone. When the temperature of thermal stimulation is 11 °C, the average rate of gas production in the experiment of thermal stimulation is less than 1/3 of that in the experiment of the combined method.     

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.     

Methane hydrate formation and an inward growing shell model in water-in-oil dispersions

Significant factors controlling gas hydrate growth in water and water-in-oil dispersions have been tested. In particular, the influence of shear rate, presence of oil, and thermodynamic driving force (represented by pressure supersaturation) on hydrate growth rates is included. Formation rates in water show some discrepancy compared to previous work, which is likely caused by differences in the apparatus geometries. A model is proposed for growth of hydrate in oil, in which a hydrate shell forms on a water droplet, followed by additional conversion of the water core to hydrate.     

Study on the kinetics of hydrate formation in a bubble column

Gas hydrate formation experiments were performed using methane in the presence of tetrahydrofuran (THF) in aqueous solution in a transparent bubble column in which a single pipe or a sintered plate was used to produce bubbles. The mole fraction of THF in aqueous solution was fixed at 6%. The hydrate formation kinetic behaviors on the surface of the rising bubble, the mechanical stability of hydrate shell formed on the surface of the bubble, the interactions among the bubbles with hydrate shell were observed and investigated morphologically. The rise velocities of individual bubbles with hydrate shells of different thickness and the consumption rates of methane gas were measured. A kinetic model was developed to correlate the experimentally measured gas consumption rate data. It was found that the hydrate formation rate on the surface of the moving bubble was high, but the formed hydrate shell was not very easy to be broken up. The bubbles with hydrate shells tended to agglomerate rather than merge into bigger bubble. This kind of characteristic of hydrate shell hindered the further formation of hydrate and led to the lower consumption rate of methane. The consumption rate of methane was found to increase with the decrease of temperature or increase of pressure. The increase of gas flux led to a linear increase in consumption rate of methane. It was demonstrated that the developed kinetic model could be used to correlate the consumption rate satisfyingly.     

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.     

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。     

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。     

多孔材料中甲烷水合物生成的传热数值模拟研究

水合物储运(NGH)是近几年发展起来的天然气储运技术,已具备实现工业化的潜力。但水合物的生长是传质传热控制的反应,因此在放大实验中存在诸多不确定因素。针对该问题,对水合物反应器中多孔材料内甲烷水合物生成传热过程建立了基于化学反应动力学和多孔材料内传质传热的甲烷水合物生成传热数学模型,可用于计算反应器内水合物生成分布和热量分布,指导水合反应器的设计和优化。通过模拟与实验数据对比验证了该模型的可靠性,并对使用了不同热导率填料的水合反应过程进行数值模拟。结果显示,模拟值与实验值的绝对平均相对误差小于6%,生成传热模型准确性高;在水合反应过程中,热量传递是影响水合物生成速率的关键因素之一。导热不良时,易在水合物生成中心部分形成局部过热,对水合物生长造成热抑制。在进行水合物生成放大实验时,应特别注意反应器内部的热量控制。     

多孔材料中甲烷水合物生成的传热数值模拟研究

水合物储运(NGH)是近几年发展起来的天然气储运技术,已具备实现工业化的潜力。但水合物的生长是传质传热控制的反应,因此在放大实验中存在诸多不确定因素。针对该问题,对水合物反应器中多孔材料内甲烷水合物生成传热过程建立了基于化学反应动力学和多孔材料内传质传热的甲烷水合物生成传热数学模型,可用于计算反应器内水合物生成分布和热量分布,指导水合反应器的设计和优化。通过模拟与实验数据对比验证了该模型的可靠性,并对使用了不同热导率填料的水合反应过程进行数值模拟。结果显示,模拟值与实验值的绝对平均相对误差小于6%,生成传热模型准确性高;在水合反应过程中,热量传递是影响水合物生成速率的关键因素之一。导热不良时,易在水合物生成中心部分形成局部过热,对水合物生长造成热抑制。在进行水合物生成放大实验时,应特别注意反应器内部的热量控制。     

Influence factors of methane hydrate formation from ice: Temperature,pressure and SDS surfactant

A series of experiments of forming hydrate from ice powders in different conditions have been carried out with constant volume method to evaluate the influence factors such as pressure, temperature, and SDS surfactant. The change of temperature and pressure were collected as a function of elapsed time, which were used to calculate the gas consumption and hydrate saturation during hydrate formation (pVT method). Based on the experimental results and the analysis, it is concluded that: (1) Both initial pressure and temperature have effect on the hydrate formation and temperature plays a more important role in the process; (2) heating and secondary pressurization will promote the gas hydrate formation and enhance the hydrate saturation as a result. Meanwhile, the promotion of heating seems to be more obvious than that of secondary pressurization; (3) different concentrations of SDS surfactant have clearly influence on the saturation of gas hydrate and there is an optimal concentration to promote the hydrate formation.     

Measurements of methane hydrate heat of dissociation using high pressure differential scanning calorimetry

The methane hydrate heat of decomposition was directly measured up to 20 MPa and 292 K using a high pressure differential scanning calorimeter (DSC). The methane hydrate sample was formed ex-situ using granular ice particles and subsequently transferred into the DSC cell under liquid nitrogen. The ice and water impurities in the hydrate sample were reduced by converting any dissociated hydrate into methane hydrate inside the DSC cell before performing the thermal properties measurements. The methane hydrate sample was dissociated by raising the temperature (0.5-1.0 K/min) above the hydrate equilibrium temperature at a constant pressure. The measured methane hydrate heat of dissociation (H→W+G), ΔH_d, remained constant at 54.44±1.45 kJ/mol gas (504.07±13.48 J/gm water or 438.54± 13.78 J/gm hydrate) for pressures up to 20 MPa. The measured ΔH_d is in agreement with the Clapeyron equation predictions at high pressures; however, the Clausius-Clapeyron equation predictions do not agree with the heat of dissociation data at high pressures. In conclusion, it is recommended that the Clapeyron equation should be used for hydrate heat of dissociation estimations at high pressures.     

甲烷+氨水体系水合物生成条件实验测定及计算

甲烷在氨水体系中生成水合物的实验数据对于开发水合法回收合成氨驰放气工艺以及操作条件的确定具有重要意义。本文测定了氨摩尔分数为1.018、3.171、5.278氨水溶液中甲烷气体水合物的生成条件。结果表明：氨的加入对甲烷水合物的生成起着明显抑制作用,而且随着氨浓度的增加,生成压力越高。采用Chen-Guo模型对甲烷在氨水中生成水合物的数据进行了计算,得到了较为满意的计算结果,平均误差为2.71%,说明Chen-Guo模型能够较好地预测该类体系的水合物的生成条件。