Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas–water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.     

Kinetics of carbon dioxide and methane hydrate formation

Experimental data on the kinetics of carbon dioxide hydrate formation and its solubility in distilled water are reported. The experiments were carried out in a semi-batch stirred tank reactor at nominal temperatures of 274, 276 and 278 K and at pressure ranging from 1.59 to 2.79 MPa for the kinetics experiments and at pressure ranging from 0.89 to 2.09 MPa for the solubility experiments. A minor inconsistency in the kinetic model developed by Englezos et al. (1987a) was removed and the model was modified to determine the intrinsic kinetic rate constant for carbon dioxide hydrate formation. The same model was also used to re-determine the intrinsic kinetic rate constant for methane hydrate formation. The model is based on the crystallization theory coupled with the two-film theory for gas absorption in the liquid phase. The Henry's constant (H) and apparent dissolution rate constant (K_La) required in the model were determined using the experimental solubility data. The kinetic model describes the experimental data very well. The kinetic rate constant obtained for the carbon dioxide hydrate formation was found to be higher than that for methane.     

Surfactant effects on hydrate formation in an unstirred gas/liquid system: An experimental study using methane and sodium alkyl sulfates

This paper reports an experimental study on the effects of surfactant additives on the formation of a clathrate hydrate in a quiescent methane/liquid-water system, which was initially composed of a 300-cm³ aqueous phase and an ∼640-cm³ methane-gas phase, then successively provided with methane such that the system pressure was held constant. The surfactants used in the present study were three sodium alkyl sulfates appreciably different in the alkyl chain length—they were sodium dodecyl sulfate (abbreviated as SDS), sodium tetradecyl sulfate (abbreviated as STS) and sodium hexadecyl sulfate (abbreviated as SHS). For each surfactant added to water up to, at most, 1.82-3.75 times the solubility, we performed visual observations of hydrate formation simultaneously with the measurements of methane uptake due to the hydrate formation. The qualitative hydrate-formation behavior thus observed was almost the same irrespective of the species as well as the initial concentration of the surfactant used; i.e., thick, highly porous hydrate layers were formed and grew on the horizontal gas/liquid interface and also on the test-chamber wall above the level of the gas/liquid interface. In each experimental operation, hydrate formation continued for a limited time (from ∼6 to ) and then practically ceased, leaving only a small proportion (typically 15% or less) of the aqueous solution unconverted into hydrate crystals. The variations in the time-averaged rate of hydrate formation (as measured by the rate of methane uptake) and the final water-to-hydrate conversion ratio with the initial concentration of each surfactant were investigated. Moreover, we examined the promotion of hydrate formation with the aid of a water-cooled cold plate, a steel-made flat-plate-type heat sink, vertically dipped into the aqueous phase across the gas/liquid interface.     

Thermodynamic consistency test for experimental data of water content of methane

Accurate knowledge of the water content of natural gases is an important factor to estimate the gas hydrate, ice, and condensed water formation conditions. However, the experimental data regarding the water content of gases in equilibrium with the gas hydrate, ice, or liquid water (near gas hydrate or ice formation region) are limited. This is partly because of the fact that concentration of water in the gaseous phase in equilibrium with gas hydrate, ice or liquid water (near gas hydrate or ice formation region) is very low considering that reaching the equilibrium conditions near and inside gas hydrate or ice formation region is time consuming process. The measurement difficulties may consequently result in generating unreliable experimental data. This work aims at performing a thermodynamic consistency test based on area approach to study the reliability of some experimental data reported in the literature on the water content of methane (the main component of natural gases) in equilibrium with the gas hydrate, ice, or liquid water (near gas hydrate or ice formation region). A discussion is made on the studied experimental data according to the performed consistency test. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Kinetics of methane hydrate formation in aqueous electrolyte solutions

Experimental data on the kinetics of methane hydrate formation in aqueous electrolyte solutions are reported. The experiments were carried out in a semi-batch stirred tank reactor in three NaCl and two KCl solutions as well as in a solution containing a mixture of NaCl and KCl at three different nominal temperatures from 270 to 274 K and at pressures ranging from 3.78 to 7.08 MPa. The kinetic model developed by Englezos et al. (1987a) was adapted to predict the growth of hydrates. The model is based on the crystallisation theory coupled with the two-film theory for gas absorption in the liquid phase. The kinetic rate constant which appears in the model was that obtained earlier for methane hydrate formation in pure water. The effect of the electrolytes was taken into account through the computation of the three-phase equilibrium conditions and the corresponding fugacities. Overall, the model predictions match the experimental data very well with the largest prediction error being less than 10%.     

不同分子模型对甲烷水合物分解微观特性表征

采用SPC/E-UA、SPC/E-AA、TIP4P-UA和TIP4P-AA分子模型研究了NVE系综下甲烷水合物的微观分解特性。对比分析了不同模型下水合物的平衡温度及分解热。研究了F₃随空间及时间的变化，对液态水-水合物的界面进行了界定。比较了不同区域的势能的变化规律，发现分解过程具有显著的非平衡传热特性。分析了水和甲烷密度的空间分布规律及逸出的甲烷分子数随时间的变化规律，发现甲烷逸出速度逐渐减小。对不同模型下分解所需的活化能进行了计算，并与实验值进行对比。对比不同区域均方位移及扩散系数发现分解呈现显著的非平衡传质特性。研究表明甲烷分子模型对分解影响甚微，而水分子模型影响较为明显，在NVE系综下通过SPC/E模型表征的平衡温度、活化能及分解热与实验值更加吻合。     

Phase behavior and structure transition of the mixed methane and nitrogen hydrates

Pure methane and nitrogen form structure I and II hydrate, respectively, and therefore the structure type of mixed gas hydrate was found to largely depend on their relative gas composition. In addition to the structural difference of size and shape, each hydrate structure shows different capacity to store the guest molecules. In this study, we investigated phase and structural behaviors according to the composition of methane+nitrogen gas mixture. Three-phase (H-Lw-V) equilibria of solid hydrate, water-rich liquid and vapor phase containing 25.24 mol%, 28.51 mol%, 31.23 mol% and 40.39 mol% of methane were determined at various temperatures (in the range from 273.30 K to 285.05 K) and pressures (from 8.325 MPa to 20.700 MPa). 13C solid-state NMR spectroscopy and powder XRD method were performed to identify the formed structure of hydrate samples. The experimental results showed that gas hydrate of the methane+nitrogen mixture changes its structure from sI to sII between 25.24 mol% and 28.51 mol% of methane concentration. These results of phase behavior and structure identification for the mixed gas hydrates are expected to be very helpful in evaluating the feasibility of exploitation of methane gas from natural gas hydrate and the separation process using gas hydrate as a storage-media     

Crystallization Mechanisms and Rates of Cyclopentane Hydrates Formation in Brine

Clathrate hydrates most often grow at the interface between liquid water and another fluid phase (hydrocarbon) acting as a provider for the hydrate guest molecules, and some transfer through this shell is required for the hydrate growth to proceed, thus self‐limiting the reaction rate. An optical microscope and a horizontal reaction cell are utilized to capture the shell growth phenomenology and to estimate the hydrate layer growth rates from sequential pictures. Cyclopentane (CP) is chosen as the hydrate‐forming molecule to obtain hydrates at low pressure. Experimental hydrate layer growth rates are provided for the CP+brine system, using various combinations of salts and degrees of subcooling.     

Growth kinetics of hydrate formation from water–hydrocarbon system

Gas hydrates have drawn global attentions in the past decades as potential energy resources. It should be noted that there are a variety of possible applications of hydrate-based technologies, including natural gas storage, gas transportation, separation of gas mixture, and seawater desalination. These applications have been critically challenged by insufficient understanding of hydrate formation kinetics. In this work, the literatures on growth kinetic behaviors of hydrate formation from water-hydrocarbon were systematically reviewed. The hydrate crystal growth, hydrate film growth and macroscopic hydrate formation in water system were reviewed, respectively. Firstly, the hydrate crystal growth was analyzed with respect to different positions, such as gas/liquid interface, liquid–liquid interface and gas–liquid–liquid system. Secondly, experimental and modeling studies on the growth of hydrate film at the interfaces between guest phase and water phase were categorized into two groups of lateral growth and thickening growth considering the differences in growth rates. Thirdly, we summarized the promoters and inhibitors reported (biological or chemical, liquid or solid and hydrophobic or hydrophilic) and analyzed the mechanisms affecting hydrate formation in bulk water system. Knowledge gaps and suggestions for further studies on hydrate formation kinetic behaviors are presented.     

Prediction of hydrate formation conditions based on the vdWP‐type models at high pressures

Prediction of phase boundaries of gas hydrates has been done for several decades based on the vdWP (van der Waals and Platteeuw) hydrate equation and the classical thermodynamic equations for describing the water fugacities in water or ice phase. This procedure gives a reasonable prediction at low pressures, but when the pressure increases, above 10⁵ kPa, it shows a significant error. In the conventional vdWP‐type models it has been assumed that the volume difference between the empty hydrate lattice and pure liquid water is independent of the system pressure and temperature. In this work, different approaches for describing the volume dependency of pure liquid water and the empty hydrate lattice on the system pressure have been used to predict the hydrate equilibria based on the vdWP‐type model. Also, an expression is introduced to estimate the volume of methane hydrate lattice as a function of pressure and temperature. Finally, this method is extended to other hydrate formers, that is, ethane, carbon dioxide, xenon, and nitrogen. The predicted values are in good agreement with the experimental data both for L_w–H–V and L_w–H–L_hf phase boundaries.     

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。     

On the Applicability of a Quasi-Stationary Solution of the Diffusion Equation for the Hydrate Layer Formed at the Gas–Ice (Water) Interface

The problem of methane hydrate formation when the process is controlled by gas diffusion in the hydrate layer formed at the gas–ice (or water) interface is solved. It is shown that an approximate quasi-stationary solution of the diffusion equation is in good agreement with its numerical solution over a wide range of the solubility of the gas in the hydrate, which is dependent on pressure. It is found that the time for the complete transition of the water (or ice) phase into the hydrate state decreases with an increase in the saturation concentration of the mobile gas in the hydrate. The kinetic equations derived based on a quasi-stationary solution of the diffusion equation, which are relationships for the intensity of hydrate formation in snow-containing (or water-containing) formations during the filtration of hydrate-forming gases, are used to describe the concentration fields of the diffusing gas and the dynamics of hydrate layer growth.     

Thermodynamic Model for Prediction of Phase Equilibria of Clathrate Hydrates in the Presence of Water-Insoluble Organic Compounds

A thermodynamic model for the prediction of pressure–temperature phase diagrams of structures II and H clathrate hydrates of methane, carbon dioxide, or hydrogen sulfide in the presence of “water-insoluble” organic componds is presented. The model is based on the equality of water fugacity in the aqueous and hydrate phases. The solid solution theory of van der Waals–Platteeuw (vdW–P) is used for calculation of the fugacity of water in the hydrate phase. The Peng–Robinson (PR) equation of state (EoS) is employed to calculate the fugacity of the components in the gas phase. It is assumed that the gas phase is water and promoter free and the organic compounds do not have marked effects on water activity in the aqueous phase. The results of this model are compared to existing experimental data from the literature. Acceptable agreement is found between the model predictions and the investigated experimental data.     

基于不同状态方程预测气体水合物相平衡条件

气相逸度的计算结果会直接影响气体水合物相平衡条件的预测精度。基于Chen-Guo模型,选取RK、SRK、PR以及PT四种状态方程计算逸度,分别对甲烷、乙烷以及二氧化碳三种不同气体水合物在不同温度范围内的相平衡条件进行计算。结果表明：纯水条件下,RK方程最适合预测甲烷水合物相平衡条件,而PR方程更适合预测乙烷及二氧化碳水合物相平衡条件;对于冰中,SRK方程适合预测甲烷水合物的相平衡条件,PR方程适合预测乙烷水合物的,而RK方程更适合二氧化碳水合物的;对于甲烷水合物,低于218.2 K的预测是导致模型预测精度偏低的原因;对于乙烷水合物,需要提高低于230.2 K的预测精度;对二氧化碳水合物而言,提高对低于270.7 K的预测可以进一步提高模型预测精度。     

油藏流体中H型水合物生成条件的计算

1 INTRODUCTION Gas hydrates are serious problems in the petroleum and petrochemical industries since it may cause the plugging of production facilities and trans- portation pipelines during gas and oil production. It is known to all that gas hydrates have three poten- tial hydrate formation structures: structure- structure- and structure-H (SH). The two for- mer structures have been studied extensively and their phase equilibrium conditions are well characterized. For a long time, molecu…     

Stability and growth of gas hydrates below the ice–hydrate–gas equilibrium line on the P–T phase diagram

Using a previously developed experimental technique, the behavior of small methane and propane hydrate samples formed from water droplets between 0.25 and 2.5 mm in size has been studied in the pressure–temperature area between the ice–hydrate–gas equilibrium line and the supercooled water–hydrate–gas metastable equilibrium line, where ice is a stable phase. The unusual persistence of the hydrates within the area bounded by these lines and the isotherms at T=253 K for methane hydrate or at T=263 K for propane hydrates was observed. This behavior has not previously been reported. For example, in the experiment carried out at 1.9 MPa and 268 K, the methane hydrates existed in a metastable state (the equilibrium pressure at 268 K is 2.17 MPa) for 2 weeks, then immediately dissociated into liquid supercooled water and gas after the pressure was isothermally decreased slightly below the supercooled water–hydrate–gas metastable equilibrium pressure. It was found that dissociation of metastable hydrate into supercooled water and gas was reversible. The lateral hydrate film growth rates of metastable methane and propane hydrates on the surface of supercooled water at a pressure below the ice–hydrate–gas equilibrium pressure were measured. The temperature range within which supercooled water formed during hydrate dissociation can exist and a role of supercooled water in hydrate self-preservation is discussed.     

Characteristics of methane hydrate formation in carbon nanofluids

When methane hydrate is formed artificially by simply reversing its process of natural generation, the amount of methane gas consumed by hydrate formation is fairly low, which is problematic for its large scale synthesis and application. Therefore, this study examined methods for increasing the amount of gas consumed by adding MWCNTs (multi-walled carbon nanotubes) and OMWCNTs (oxidized multi-walled carbon nanotubes). The surfaces of the MWCNTs were oxidized chemically, and dispersed uniformly in distilled water after a dispersion operation. The amount of methane gas consumed during the formation of methane hydrate in the oxidized carbon nanofluid was approximately 4.5 times higher than that in distilled water. The hydrate-nanocarbon fluid phase boundary line was shifted to the right side of the hydrate-pure water phase boundary line in the pressure–temperature phase diagram. The carbon nanofluid system accelerated the rate of methane hydrate formation at low subcooling temperatures (<8 K).     

Equilibrium and Kinetic Properties of Methane Hydrate

During methane dissolution in water in a closed space, the pressure varies exponentially with time until the formation of methane hydrate. A model of this process is proposed that fits experimental data well. The methane concentration at the onset of hydrate formation is calculated as a function of temperature and pressure.     

Theoretical pressure dependency of carbon dioxide solubility under hydrate–liquid water equilibrium

The effect of pressure on carbon dioxide solubility in water is significantly smaller than that of temperature under hydrate–liquid water (H–L_w) equilibrium. As a result, experimental values of carbon dioxide solubility in the water rich liquid phase under H–L_w equilibrium are often inconclusive and in some cases contradictory. This work proposes a theoretical derivation, based on fundamental thermodynamics, of the gas hydrate former solubility dependency on pressure for any binary system under two‐phase equilibrium. The obtained expression is applied to the carbon dioxide–water system under both hydrate–liquid water and vapour–liquid water equilibrium. It is shown that the solubility of carbon dioxide in the water rich liquid phase increases with increasing pressure under H–L_w equilibrium. The predicted trend is then compared to the limited experimental data available in the literature.     

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.