The methane hydrate formation and the resource estimate resulting from free gas migration in seeping seafloor hydrate stability zone

It is a typical multiphase flow process for hydrate formation in seeping seafloor sediments. Free gas can not only be present but also take part in formation of hydrate. The volume fraction of free gas in local pore of hydrate stable zone (HSZ) influences the formation of hydrate in seeping seafloor area, and methane flux determines the abundance and resource of hydrate-bearing reservoirs. In this paper, a multiphase flow model including water (dissolved methane and salt)-free gas hydrate has been established to describe this kind of flow-transfer-reaction process where there exists a large scale of free gas migration and transform in seafloor pore. In the order of three different scenarios, the conversions among permeability, capillary pressure, phase saturations and salinity along with the formation of hydrate have been deducted. Furthermore, the influence of four sorts of free gas saturations and three classes of methane fluxes on hydrate formation and the resource has also been analyzed and compared. Based on the rules drawn from the simulation, and combined information gotten from drills in field, the methane hydrate(MH) formation in Shenhu area of South China Sea has been forecasted. It has been speculated that there may breed a moderate methane flux below this seafloor HSZ. If the flux is about 0.5 kg m-2 a-1, then it will go on to evolve about 2700 ka until the hydrate saturation in pore will arrive its peak (about 75%). Approximately 1.47 109 m3 MH has been reckoned in this marine basin finally, is about 13 times over preliminary estimate.

Gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, Northern South China Sea

Based on the comprehensive interpretation and study of the Neogene fracture system and diapiric structure, it can be concluded that the diapiric structures, high-angle fractures and vertical fissure system are the main gas-bearing fluid influx sub-system for gas hydrate geological system in Shenhu Area, northern South China Sea. The Neogene fractures widely developed in the study area may be classed into two groups: NW (NNW)-trending and NE (NNE)-trending. The first group was active in the Late Miocene, while the second one was active since the Pliocene. The NE (NNE)-trending fractures were characterized by lower activity strength and larger scale, and cut through the sediment layers deposited since the Pliocene. Within the top sediment layers, the high-angle fracture and vertical fissure system was developed. The diapiric structures display various types such as a turtle-back-like arch, weak piercing, gas chimney, and fracture (or crack, fissure). On the seismic profile, some diapiric structures show the vertical chimney pathway whose top is narrow and the bottom is wide, where some ones extend horizontally into pocket or flower-shaped structures and formed the seismic reflection chaotic zones. Within the overlying sediment layers of the diapiric structure, the tree branch, flower-shaped high-angle fractures and vertical fissures were developed and became the pathway and migration system of the gas-bearing fluid influx. In the study area, the diapiric structures indicate a high temperature/over pressure system ever developed. Closely associated and abundant bright-spots show the methane-bearing fluid influx migrated vertically or horizontally through the diapiric structures, high-angle fractures and vertical fissures. In the place where the temperature and pressure conditions were favor for the formation of gas hydrate, the hydrate reservoir deposition sub-system was developed.

Influence of 5A-Type Zeolite Powder on Tetrahydrofuran Hydrate Formation and Dissociation Process

Visual observations of tetrahydrofuran (THF) hydrate formation and dissociation processes with 5A-type zeolite powder were made at normal atmospheric conditions and below zero temperature by microscope. Results indicate that 5A-type zeolite powder can promote THF hydrate growth. At the same time, in the presence of 5A-type zeolite, agglomerated crystals and vein-like crystals of THF hydrate were also formed. SA-type zeolite powder increases the crystallization temperature and decreases the dissociation temperature. The particle size distribution of 5A-type zeolite powder influences THF hydrate formation and its dissociation characteristics significantly.

Study on the Dissociation Behavior of Gas Hydrate in Porous Sediment Based on Fractal Theory

The dissociation process of gas hydrate was regarded as a gas-solid reaction without solid production layer when the temperature was above the zero centigrade. Based on the shrinking core model and the fractal theory, a fractional dimension dynamical model for gas hydrate dissociation in porous sediment was established. The new approach of evaluating the fractal dimension of the porous media was also presented. The fractional dimension dynamical model for gas hydrate dissociation was examined with the previous experimental data of methane hydrate and carbon dioxide hydrate dissociations, respectively. The calculated results indicate that the fractal dimensions of porous media acquired with this method agree well with the previous study. With the absolute average deviation (AAD) below 10%, the present model provided satisfactory predictions for the dissociation process of methane hydrate and carbon dioxide hydrate.

Experimental Investigation on Propane Hydrate Dissociation by High Concentration Methanol and Ethylene Glycol Solution Injection

The dissociation behaviors of propane hydrate by high concentration alcohols inhibitors injection were investigated. Methanol (30.0, 60.1, 80.2, and 99.5 wt %) and ethylene glycol (30.0, 60.1, 69.8, 80.2, and 99.5 wt %) solution were injected, respectively, as alcohols inhibitors in 3.5 L transparent reactor. It is shown that the average dissociation rates of propane hydrate injecting methanol and ethylene glycol solution are 0.02059-0.04535 and 0.0302-0.0606 mol.min(-1).L-1, respectively. The average dissociation rates increase with the mass concentration increase of alcohols solution, and it is the biggest when 99.5 wt % ethylene glycol solution was injected. The presence of alcohols accelerates gas hydrate dissociation and reduces the total need of external energy to dissociate the hydrates. Density differences act as driving force, causing the acceleration effects of ethylene glycol on dissociation behaviors of propane hydrate are better than that of methanol with the same injecting flux and mass concentration.

Methane hydrate growth velocity in seepage system of Qiongdongnan Basin, South China Sea

The occurrences of diapirs, gas-filled zones and gas plumes in seawater in Qiongdongnan Basin of South China Sea indicate that there may exist seepage system gas-hydrate reservoirs. Assuming there has a methane venting zone of 1500 m in diameter, and the methane flux is 1000 kmol/a, and the temperature of methane hydrate-bearing sediments ranges from 3 degrees C to 20 degrees C, then according to the hydrate film growth theory, by numerical simulation, this paper computes the temperatures and velocities in 0 mbsf, 100 mbsf, 200 mbsf, 425 mbsf over discrete length, and gives the change charts. The results show that the cementation velocity in sediments matrix of methane hydrate is about 0.2 nm/s, and the seepage system will evolve into diffusion system over probably 35000 years. Meanwhile, the methane hydrate growth velocity in leakage system is 20 similar to 40 times faster than in diffusion system.

Molecular Dynamics Simulation of Methane Hydrate Dissociation Process in the Presence of Thermodynamic Inhibitor

The dissociation of methane hydrate in the presence of ethylene glycol (11.45 mol.L-1) at 277.0 K was studied using canonical ensemble (NVT) molecular dynamics simulations. Results show that hydrate dissociation starts from the surface layer of the solid hydrate and then gradually expands to the internal layer. Thus, the solid structure gradually shrinks until it disappears. A distortion of the hydrate lattice structure occurs first and then the hydrate evolves from a fractured frame to a fractional fragment. Finally, water molecules in the hydrate construction exist in the liquid state. The inner dissociating layer is, additionally, coated by a liquid film formed from outer dissociated water molecules outside. This film inhibits the mass transfer performance of the inner molecules during the hydrate dissociation process.

Effect of microwave on formation/decomposition of natural gas hydrate

Natural gas hydrate (NGH) reservoirs have been considered as a substantial future clean energy resource and how to recover gas from these reservoirs feasibly and economically is very important. Microwave heating will be taken as a promising method for gas production from gas hydrates for its advantages of fast heat transfer and flexible application. In this work, we investigate the formation/decomposition behavior of natural gas hydrate with different power of microwave (2450MHZ), preliminarily analyze the impact of microwave on phase equilibrium of gas hydrate,and make calculation based on van der Waals-Platteeuw model. It is found that microwave of a certain amount of power can reduce the induction time and sub-cooling degree of NGH formation, e.g., 20W microwave power can lead to a decrease of about 3A degrees C in sub-cooling degree and the shortening of induction time from 4.5 hours to 1.3 hours. Microwave can make rapid NGH decomposition, and water from NGH decomposition accelerates the decomposition of NGH with the decomposition of NGH. Under the same pressure, microwave can increase NGH phase equilibrium temperature. Different dielectric properties of each composition of NGH may cause a distinct difference in temperature in the process of NGH decomposition. Therefore, NGH decomposition by microwave can be affected by many factors.

Experimental Investigation into the Production Behavior of Methane Hydrate in Porous Sediment with Hot Brine Stimulation

The gas production behavior from methane hydrate in porous sediment by injecting the brine with the salinity of 0−24 wt % and the temperature of −1 to 130 °C was investigated in a one-dimensional experimental apparatus. The results show that the gas production process consists of three periods: the free gas production, the hydrate dissociation, and the general gas reservoir production. The hydrate dissociation accompanies the temperature decrease with the injection of the brine (NaCl solution), and the dissociation duration is shortened with the increase of the salinity. With the injection of hot brine, instantaneous hydrate dissociation rate also increases with the increase of the salinity. However, while the NaCl concentration is beyond a certain value, the rate has no longer continued increasing. Thermal efficiency and energy ratio for the hydrate production can be enhanced by injecting hot brine, and the enhanced effectiveness is quite good with the injection of high salinity at lower temperature.

In situ hydrate dissociation using microwave heating: Preliminary study

In this work, we investigate the dissociation behavior of natural gas hydrate in a closed system with microwave (MW) heating and hot water heating. The hydrate was formed at temperatures of 1-4 degrees C and pressures of 4.5-5.5 MPa. It was found that the gas hydrate dissociated more rapidly with microwave than with hot water heating. The rate of hydrate dissociation increased with increasing microwave power, and it was a function of microwave power. Furthermore, the temperature of the hydrate increased linearly with time during the microwave radiation.

Replacement of methane from quartz sand-bearing hydrate with carbon dioxide-in-water emulsion

The replacement of CH4 from its hydrate in quartz sand with 90:10, 70:30, and 50:50 (W-CO2:W-H2O) carbon dioxide-in-water (C/W) emulsions and liquid CO2 has been performed in a cell with size of empty set 36 x 200 mm. The above emulsions were formed in a new emulsifier, in which the temperature and pressure were 285.2 K and 30 MPa, respectively, and the emulsions were stable for 7-12 h. The results of replacing showed that 13.1-27.1%, 14.1-25.5%, and 14.6-24.3% of CH4 had been displaced from its hydrate with the above emulsions after 24-96 It of replacement, corresponding to about 1.5 times the CH4 replaced with high-pressure liquid CO2. The results also showed that the replacement rate of CH4 with the above emulsions and liquid CO2 decreased from 0.543, 0.587, 0.608, and 0.348 1/h to 0.083, 0.077, 0.069, and 0.063 1/h with the replacement time increased from 24 to 96 h. It has been indicated by this study that the use of CO2 emulsions is advantageous compared to the use of liquid CO2 in replacing CH4 from its hydrate.

Experimental study on flow characters of CH3CCl2F hydrate slurry

The flow behaviors of CH3CCl2F hydrate slurry with volume concentration of 10-70% were studied in a new built flow loop with a diameter of 42.0 mm and length of 30.0 m. Morphologies of the fluids from slurrylike hydrates to slushlike hydrates with increasing of hydrate volume concentration in pipeline were observed. Pressure drops in pipeline also were studied and an exceptional pressure transition zone with hydrate volume concentration between 30% and 40% was found for the first time, which can be used as a notation to judge if the pipeline runs safely or not. Fanning friction factors of the hydrate slurries with all hydrate contents tend to constants between 0.38 and 0.5, which depend on the volume concentration in slurries, when the velocity reaches 1.5 m/s. A simple relation to estimate the pressure drop of hydrate slurry in pipeline was presented and verified. Experimental results were compared to the estimated results, which showed a good agreement. 

Influence of 3A molecular sieve to tetrahydrofuran(THF) hydrate formation

Visual observation of the THF hydrate formation process in the presence of a 3A molecular sieve has been made at normal atmosphere and below a temperature of zero by microscopy. The results indicate that a 3A molecular sieve can induce the nucleation of the THF hydrate and promote the THF hydrate growth. With the existence of a 3A molecular sieve, the growth rate of THF hydrate is between 0.01 and 0.05 mu m/s. In comparison with the system without any 3A molecular sieve, the growth rate increases about 4 nm/s. After the THF hydrate grows into megacryst, the crystals will recombine and partially change under the same condition.

Use of electrical resistance to detect the formation and decomposition of methane hydrate

The changes of electrical resistance (R) were studied experimentally in the process of CH4 hydrate formation and decomposition, using temperature and pressure as the auxiliary detecting methods simultaneously. The experiment results show that R increases with hydrate formation and decreases with hydrate decompositon. R is more sensitive to hydrate formation and decompositon than temperature or pressure, which indicates that the detection of R will be an effective means for detecting natural gas hydrate (NGH) quantitatively.

Determination of appropriate condition on replacing methane from hydrate with carbon dioxide

This paper is intended to determine the appropriate conditions for replacing CH4 from NGH with CO2. By analyzing the hydration equilibrium graphs and geotherms, the HSZs of NGH and CO2 hydrate, both in permafrost and under deep sea, were determined. Based on the above analysis and experimental results, it is found that to replace CH4 from NGH with gaseous CO2, the appropriate experimental condition should be in the area surrounded by four curves: the geotherm, (H-V)(CO2), (L-V)(CO2) and (H-V)(CH4), and to replace CH4 from NGH with liquid CO2, the condition should be in the area surrounded by three curves: (L-V)(CO2), (H-L)(CO2) and (H-V)CH4. For conditions in other areas, either CO2 can not form a hydrate or CH4 can release little from its hydrate, which are not desirable results.