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.

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.

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. 

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.

Experimental investigation of production behavior of methane hydrate under ethylene glycol injection in unconsolidated sediment

This article investigates the gas production behavior from methane hydrate (MH) in porous sediment by injecting ethylene glycol (EG) solution with the different concentrations and the different injection rates in an one-dimensional experimental apparatus. The results suggest that the gas production process can be divided into the four stages: (1) the initial injection, (2) the EG diluteness, (3) the hydrate dissociation, and (4) the remained gas output. Nevertheless, the water production rate keeps nearly constant during the whole production process. The production efficiency is affected by both the EG concentration and the EG injection rate, and it reaches a maximum with the EG concentration of 60 wt %.

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.

Analysis for temperature and pressure fields in process of hydrate dissociation by depressurization

An improved axisymmetric mathematic modeling is proposed for the process of hydrate dissociation by depressurization around vertical well. To reckon in the effect of latent heat of gas hydrate at the decomposition front, the energy balance equation is employed. The semi-analytic solutions for temperature and pressure fields are obtained by using Boltzmann-transformation. The location of decomposition front is determined by solving initial value problem for system of ordinary differential equations. The distributions of pressure and temperature along horizontal radiate in the reservoir are calculated. The numeric results indicate that the moving speed of decomposition front is sensitively dependent on the well pressure and the sediment permeability. Copyright (C) 2010 John Wiley & Sons, Ltd.

Genetic model of the hydrate system in the fine grain sediments in the northern continental slope of South China Sea

Gas hydrate samples were obtained firstly in China by drilling on the northern margin of South China Sea (SCS). To understand the formation mechanism of this unique accumulation system, this paper discusses the factors controlling the formation of the system by accurate geophysical interpretation and geological analysis, based on the high precision 2-D and 3-D multichannel seismic data in the drilling area. There are three key factors controlling the accumulation of the gas hydrate system in fine grain sediment: (1) large volume of fluid bearing methane gas Joins the formation of gas hydrate. Active fluid flow in the northern South China Sea makes both thermal gas and/or biogenic gas migrate into shallow strata and form hydrate in the gas hydrate stability zone (GHSZ). The fluid flow includes mud diapir and gas chimney structure. They are commonly characterized by positive topographic relief, acoustic turbidity and push-down, and low reflection intensity on seismic profiles. The gas chimneys can reach to GHSZ, which favors the development of BSRs. It means that the active fluid flow has a close relationship with the formation and accumulation of gas hydrate. (2) The episodic process of fracture plays an important role in the generation of gas hydrate. It may provide the passage along which thermogenic or biogenic gas migrated into gas hydrate stability zone (GHSZ) upward. And it increases the pore space for the growth of hydrate crystal. (3) Submarine landslide induced the anomalous overpressure activity and development of fracture in the GHSZ. The formation model of high concentration gas hydrate in the drilling sea area was proposed on the basis of above analysis.

Gas seepage on the sea floor of Okinawa Trough Miyako Section

A marine geophysical survey was carried out, on the RN Science 1 of the Institute of Oceanography, Chinese Academy of Sciences (IOCAS), in 2000, at the Miyako Section of Okinawa Trough. Here we present seismic and acoustic evidence of a gas seep on the sea floor on the western part of the Okinawa Through, near the lower slope of the East China Sea Slope and discuss the possibility of related formation of gas hydrate. A gas column reflection was observed in echo-sounder data above a section where the sea floor reflector was missing, on both the echo-sounder and the seismic data for line H14. The seismic data also show an acoustic curtain reflection and a turbidity reflection at this section. These anomalies are the evidence of the existence of a gas seep, which occupies an area 2.2 km in diameter. Based on the acoustic curtain on line H14, we believe that the amount of gas contained in the sediments below the gas seep is larger than 1 % by volume of sediment. Tectonically, the gas seep developed in a small basin controlled by basement uplift in the north, south and east. The thickness of the sediment layer can be greater than 3.5 km. A mud diapir structure was found in layer D beneath the gas seep. Over-pressure may occur due to the large sediment thickness and also the tectonic basement uplift in the north, south, and east. The mud diapir could be the preferential pathway for methane-rich fluids. The acoustic curtain may indicate that free gas related to the gas seep can be formed on the sea floor. We also note that the layer above the acoustic curtain on profile H14 may contain gas hydrate.

The characteristics of fluid potential in mud diapirs associated with gas hydrates in the Okinawa Trough

Many mud diapirs have been identified in the southern Okinawa Trough from a seismic survey using R/V KEXUE I in 2001. The movement and accumulation of free gas related to mud diapirs are discussed in detail by an analysis of fluid potential which is based upon velocity data. It can be found that free gas moves from the higher fluid potential strata to the lower ones and the gas hydrate comes into being during free gas movement meeting the proper criteria of temperature and pressure. In fact, gas hydrates have been found in the upper layers above the mud diapirs and in host rocks exhibiting other geophysical characteristics. As the result of the formation of the gas hydrate, the free gas bearing strata are enclosed by the gas hydrate bearing strata. Due to the high pressure anomalies of the free gas bearing strata the fluid potential increases noticeably. It can then be concluded that the high fluid potential anomaly on the low fluid potential background may be caused by the presence of the free gas below the gas hydrate bearing strata.

U/Th systematics of authigenic carbonates and d18O records from Hydrate Ridge, off the coast of Oregon, USA

Uranium (U) concentrations and activity ratios (d234U) of authigenic carbonates are sensitive recorders of different fluid compositions at submarine seeps of hydrocarbon-rich fluids ("cold seeps") at Hydrate Ridge, off the coast of Oregon, USA. The low U concentrations (mean: 1.3 ± 0.4 µg/g) and high 234U values (165-317 per mil) of gas hydrate carbonates reflect the influence of sedimentary pore water indicating that these carbonates were formed under reducing conditions below or at the seafloor. Their 230Th/234U ages span a time interval from 0.8 to 6.4 ka and cluster around 1.2 and 4.7 ka. In contrast, chemoherm carbonates precipitate from marine bottom water marked by relatively high U concentrations (mean: 5.2 ± 0.8 µg/g) and a mean d234U ratio of 166 ± 3 per mil. Their U isotopes reflect the d234U ratios of the bottom water being enriched in 234U relative to normal seawater. Simple mass balance calculations based on U concentrations and their corresponding d234U ratios reveal a contribution of about 11% of sedimentary pore water to the bottom water. From the U pore water flux and the reconstructed U pore water concentration a mean flow rate of about 147 ± 68 cm/a can be estimated. 230Th/234U ages of chemoherm carbonates range from 7.3 to 267.6 ka. 230Th/234U ages of two chemoherms (Alvin and SE-Knoll chemoherm) correspond to time intervals of low sealevel stands in marine isotope stages (MIS) 2, 4, 5, 6, 7 and 8. This observation indicates that fluid flow at cold seep sites sensitively reflects pressure changes of the hydraulic head in the sediments. The d18OPDB ratios of the chemoherm carbonates support the hypothesis of precipitation during glacial times. Deviations of the chemoherm d18O values from the marine d18O record can be interpreted as to reflect temporally and spatially varying bottom water and/or vent fluid temperatures during carbonate precipitation between 2.6 and 8.6°C.