水合物法分离低浓度煤层气中的甲烷

向模拟煤层气(13.11vol% CH4+86.89vol% N2)中添加5.8mol%四氢呋喃(THF)?0.03mol%十二烷基硫酸钠(SDS)促进剂溶液分离提纯煤层气,考察了压力、温度、反应时间对气体消耗量、反应速率、分解气中甲烷浓度、甲烷回收率和甲烷分离因子的影响,采用色谱分析法分别测定了CH4在剩余气相和分解气相中的浓度。结果表明,压力增加,CH4回收率增大,CH4分离因子增大,CH4分离效果越好;温度是影响甲烷分离因子的关键因素,温度降低,氮气和甲烷竞争进入水合物晶体中,导致水合物相中甲烷浓度降低;温度升高有利于提高水合物对甲烷的选择性。甲烷回收效率最高可达98.65%,分离因子最大为14.83。随反应时间增加,分解气中CH4浓度升高。     

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.     

One‐dimensional productivity assessment for on‐field methane hydrate production using CO2/N2 mixture gas

The direct recovery of methane from gas hydrate‐bearing sediments is demonstrated, where a gaseous mixture of CO₂ + N₂ is used to trigger a replacement reaction in complex phase surroundings. A one‐dimensional high‐pressure reactor (8 m) was designed to test the actual aspects of the replacement reaction occurring in natural gas hydrate (NGH) reservoir conditions. NGH can be converted into CO₂ hydrate by a “replacement mechanism,” which serves double duty as a means of both sustainable energy source extraction and greenhouse gas sequestration. The replacement efficiency controlling totally recovered CH₄ amount is inversely proportional to CO₂ + N₂ injection rate which directly affecting solid ‐ gas contact time. Qualitative/quantitative analysis on compositional profiles at each port reveals that the length more than 5.6 m is required to show noticeable recovery rate for NGH production. These outcomes are expected to establish the optimized key process variables for near future field production tests. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1004–1014, 2015     

Extraction of methane hydrate energy by carbon dioxide injection-key challenges and a paradigm shift

Significant effort including field work has been devoted to develop a natural gas extraction technology from natural gas hydrate reservoirs through the injection of carbon dioxide. Natural gas hydrate is practically methane hydrate. The hypothesis is that carbon dioxide will be stored as hydrate owing to its favorable stability conditions compared to methane hydrate. Although the dynamics of the CO₂/CH₄ exchange process are not entirely understood it is established that the exchange process is feasible. The extent is limited but even if the CH₄ recovery is optimized there is a need for a CH₄/CO₂ separation plant to enable a complete cyclic sequence of CO₂ capture, injection and CH₄ recovery. In this paper we propose an alternative paradigm to the Inject (CO₂)/Exchange with (CH₄)/Recover (CH₄) one namely Recover (CH₄) first and then Inject (CO₂) for Storage.     

An investigation into the laboratory method for the evaluation of the performance of kinetic hydrate inhibitors using superheated gas hydrates

Kinetic hydrate inhibitors (KHIs) are used to prevent gas hydrate formation in gas and oilfield operations. Recently, a new KHI test method was reported in which hydrates are formed and re-melted just above the equilibrium temperature, before the fluids are re-cooled and the performance of the chemical as a KHI is determined. The method, which we have called the superheated hydrate test method, is claimed to be more reliable for KHI ranking in small equipment, giving less scattering in the hold time data due to avoiding the stochastic nature of the first hydrate formation. We have independently investigated this superheated hydrate test method in steel and sapphire autoclave tests using a gas mixture forming Structure II hydrates and a liquid hydrocarbon phase, which was necessary for satisfactory results. Our results indicate that hold times are shorter than using non-superheated hydrate test methods, but they are more reproducible with less scattering. The reduced scattering occurs in isothermal or slow ramping experiments even when the hydrates are melted at more than 10 °C above the equilibrium temperature (T_eq). However, if a rapid cooling method is used, the improved reproducibility is retained when melting hydrate at 2.4 °C above T_eq but lost when warming to 8.4 °C above T_eq. Using the ramping test method, most, but not all the KHIs tested agreed with the same performance ranking obtained using traditional non-superheated hydrate test methods. This may be related to the variation in the dissociation temperature of gas hydrates with different KHIs and different KHI inhibition mechanisms. Results also varied between different size autoclave equipments.     

甲烷水合物分解实验

在体积10 L的静态反应器中研究了水合物分解动力学,考察了储存温度和水合物量等因素对水合物分解的影响。实验结果表明,水合物在273.15 K以下时存在一种异常的自我保护效应,其在268.05 K时分解速度最慢;而水合物的储运压力与储罐中的水合物量有关,当储罐容积一定时,分解压力随着储罐中水合物量的增加而增加,但水合物的分解百分比随着水合物量的增加而减少;最后提出了在一定压力下储运水合物的方法。以期为水合物法固态储存气体技术的工业化应用提供实验数据和理论依据。     

Dual Effect of Low‐Dosage Poly(Ethylene Oxides) on Methane Hydrate Formation

Time‐dependent isochoric formation of methane hydrate was investigated in the presence of low‐dose poly(ethylene oxides) (PEOs). The effect of different molecular weights of PEO on methane hydrate nucleation time and storage capacity was studied and compared. Kinetic measurements revealed a dual effect of PEO, including inhibition and stabilization effects, on methane hydrate formation. The nature and type of the effect arises from the difference in molecular weights and concentration ranges of PEOs. These parameters directly affect the nucleation time and storage capacity of methane hydrate. Generally, in comparison with pure water, PEO improved the storage capacity of methane hydrate. PEO (1000 kD) at a concentration of 0.5 wt % exhibits a significant kinetic inhibitory performance. However, it was an efficient low‐dosage hydrate stabilizer at a concentration of 0.25 wt %, along with producing gas‐rich methane hydrate suitable for gas fuel storage and transportation.     

Structure and thermal expansion of natural gas clathrate hydrates

We report on the structural properties of natural gas hydrate crystals from the Sea of Okhotsk. Using powder X-ray diffraction (PXRD), it was determined that sediments from four locations contained type I gas hydrate, which encage mostly methane (96-98%) and a small amount of carbon dioxide. For all hydrates, the lattice constant was estimated to be at 113 K, which approximately equals that of pure methane hydrate. The result is in good agreement with the structure of artificially synthesized methane + carbon dioxide mixed-gas hydrates. These results suggest that the lattice constant of the natural gas hydrate does not change due to a change of CO₂ gas content. In addition, the thermal expansion of the sampled hydrate was measured for the temperature range of 83-173 K, and the resulting density of the hydrate crystal at 273 K was estimated to be . These results are essential for applying natural gas hydrates as an alternative natural fuel resources.     

The gas-adsorption mechanism of kinetic hydrate inhibitors

Molecular dynamics was employed to study the inhibition mechanism of vinyl lactam-based kinetic hydrate inhibitors (KHIs). By comparing the inhibition functions of the same KHIs at different initial locations, we found that the KHI molecules on the surface of hydrate nuclei could obviously prolong the hydrate induction time and exhibited the best inhibition effect. The impacts of KHIs on the methane migration and the arrangement of H₂O molecules were analyzed at the molecular level. A gas-adsorbing mechanism for KHIs (i.e., the KHIs with an excellent gas adsorption ability could reduce the supersaturation of methane in the aqueous solution, reinforce the migration resistance of methane to the nucleus, and further inhibit the hydrate growth) was proposed. In addition, the conformations of KHI polymer molecules in the aqueous solution are closely related to their inhibitory effect, that is, stretched skeletons and well-organized structures would maximize their inhibitory effect.     

甲烷水合物分解动力学

根据两种测量水合物分解动力学的方法———恒定分解压力法及压力变化法 ,采用气体水合物静力学实验装置测定了甲烷水合物的分解动力学数据 .由建立的分解动力学模型计算了甲烷水合物的分解速率 ,较好地拟合了所测得的实验数据 .实验数据验证了分解速率和水合物平衡压力下的逸度与实验压力下的逸度之差有关 ,计算的分解活化能为 73.3kJ·mol^-1(甲烷 ) .     

甲烷水合物储气实验研究

1 INTRODUCTION Methane gas hydrates (MGH) are solid phase crystalline inclusion compounds (also called clathrates) that consist of a host water lattice with cavities in which methane gas is caged as a guest gas.Methane gas hydrate might contain 164 volumes (at standard pressure and temperature)of methane and 0.87 volumes of water per volume hydrate.     

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。     

第一类水合物藏降压开采实验模拟

我国南海含下伏游离气的水合物储层具有实现下伏游离气和水合物分解气“两气合采”的地质条件,开采该类型水合物藏能够增加产气量,提高经济性。但目前该类型储层的开采模拟室内实验研究较少,开采规律认识不足。本文采用实验室自行搭建的三维水合物模拟装置,建立了一套含有游离气层的第一类水合物储层制备新方法,研究了水合物藏降压开采过程的产气产水特性。结果表明,采用甲烷水合物四相点以下的生产压力能有力地加快水合物分解进程,提高开采效率,当开采压力从2.95MPa降低到2.14MPa,快速产气阶段气体采收率增加10%,总开采时间缩短约38%,总采收率从73%提高到81%。当开采井井孔位于水合物层时,可能会在井孔附近出现水合物二次生成现象,从而导致开采产气速率显著降低,相比于开采井井孔位于气层,相同累积产气量的情况下生产时间延长30%左右。对比第一、三类水合物藏发现,第一类水合物藏的快速产气阶段持续20min以上,比第三类水合物藏延长一倍多,但总的气体采收率稍低。本文塑造的是气饱和的第一类水合物藏,对实际海洋水合物藏的模拟具有一定局限性,今后研究还需从实验装置尺度、分区控温方法、实验介质筛选、储层重塑稳定性等方面着手,解决储层重塑关键技术问题,为我国含下伏游离气的泥质粉砂型天然气水合物藏开采提供基础数据参考。     

EXPERIMENTAL INVESTIGATION ON GAS HYDRATE FORMATION IN PRESENCE OF ADDITIVE COMPONENTS

Additives were used to increase gas hydrate formation rate and storage capacity. Experimental tests of methane hydrate formation were carried out in surfactant water solutions in a high-pressure cell. Sodium dodecyl sulfate (SDS) and alkyl polysaccharide glycoside (APG) were used to increase hydrate formation. The effect of SDS on hydrate formation is more pronounced compared APG. Cyclopentane (CP) also improves hydrate formation rates while it cannot increase methane gas storage capacity.     

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.     

水合物降压分解的实验及数值模拟

在天然气水合物一维分解模拟系统上进行模拟多孔介质中水合物降压分解的实验。在考虑天然气水合物分解动力学机理以及流体渗流模型的基础上;建立天然气水合物降压分解的数学模型。利用模型对降压实验进行拟合;获得了多孔介质内水合物分解本征速度常数数量级为10 mol·m^-2·Pa^-1·s^-1;比文献中测定的纯水中水合物分解本征速度常数低3个数量级。对模型进行了参数分析;发现对于实验室规模的一维系统;分解动力学过程控制整个分解过程;而对于现场规模的水合物藏;整个开采过程受水合物藏流动特性的控制;而受水合物分解过程的影响较小。     

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.     

Effect of surface curvature and wettability on nucleation of methane hydrate

Natural gas hydrate nucleation is a complex physical and chemical process that is not well understood presently. In this article, an improved thermodynamic model is proposed to analyze the effects of surface curvature and wettability on methane hydrate nucleation for the first time. The results indicate that methane hydrate nucleation is more difficult on hydrophilic curvature surfaces under the same conditions, with a larger critical nucleation radius and required energy barrier than on hydrophobic surfaces. Furthermore, a convex surface is more favorable for forming methane hydrate under the same conditions than a concave surface. The model's results are critical in elucidating the microscopic mechanism of methane hydrate nucleation and providing a theoretical foundation for developing technologies for strengthening and inhibiting hydrate formation.     

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.     

Induction time,storage capacity,and rate of methane hydrate formation in the presence of SDS and silver nanoparticles

In this communication, the kinetic parameters of methane hydrate formation (induction time, quantity and rate of gas uptake, storage capacity (SC), and apparent rate constant) in the presence of sodium dodecyl sulfate (SDS), synthetized silver nanoparticles (SNPs), and mixture of SDS?+?SNPs have been studied. Experimental measurements were performed at temperature of 273.65?K and initial pressure of 7?MPa in a 460?cm³ stirred batch reactor. Our results show that adding SDS, SNPs and their mixture increases the quantity of gas uptake, water to hydrate conversion, and SC of methane hydrate formation, noticeably. Using 300?ppm SDS increases the SC and the quantity of methane uptake 615, and 770%, respectively, compared with pure water. Investigating the hydrate growth rate at the start of hydrate formation process shows that, using SNPs, SDS, and their mixture increases the initial apparent rate constant of hydrate rate, considerably. Our results show that the system of methane?+?water?+?SDS 500?ppm?+?SNPs 45?µM represents the maximum value of initial apparent rate constant, compared with other tested systems.