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.

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 %.

Hydrate dissociation conditions for gas mixtures containing carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons using SAFT

A new method, a molecular thermodynamic model based on statistical mechanics, is employed to predict the hydrate dissociation conditions for binary gas mixtures with carbon dioxide, hydrogen, hydrogen sulfide, nitrogen, and hydrocarbons in the presence of aqueous solutions. The statistical associating fluid theory (SAFT) equation of state is employed to characterize the vapor and liquid phases and the statistical model of van der Waals and Platteeuw for the hydrate phase. The predictions of the proposed model were found to be in satisfactory to excellent agreement with the experimental data.

Control mechanisms for gas hydrate production by depressurization in different scale hydrate reservoirs

The methane hydrate was formed in a pressure vessel 38 mm in id and 500 mm in length. Experimental works on gas production from the hydrate-bearing core by depressurization to 0.1, 0.93, and 1.93 MPa have been carried out. The hydrate reservoir simulator TOUGH-Fx/Hydrate was used to simulate the experimental gas production behavior, and the intrinsic hydration dissociation constant (K-0) fitted for the experimental data was on the order of 104 mol m(-2) Pa-1 s(-1), which was one order lower than that of the bulk hydrate dissociation. The sensitivity analyses based on the simulator have been carried out, and the results suggested that the hydrate dissociation kinetics had a great effect on the gas production behavior for the laboratory-scale hydrate-bearing core. However for a field-scale hydrate reservoir, the flow ability dominated the gas production behavior and the effect of hydrate dissociation kinetics on the gas production behavior could be neglected.

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.

Thermally induced evolution of phase transformations in gas hydrate sediment

Thermally induced evolution of phase transformations is a basic physical-chemical process in the dissociation of gas hydrate in sediment (GHS). Heat transfer leads to the weakening of the bed soil and the simultaneous establishment of a time varying stress field accompanied by seepage of fluids and deformation of the soil. As a consequence, ground failure could occur causing engineering damage or/and environmental disaster. This paper presents a simplified analysis of the thermal process by assuming that thermal conduction can be decoupled from the flow and deformation process. It is further assumed that phase transformations take place instantaneously. Analytical and numerical results are given for several examples of simplified geometry. Experiments using Tetra-hydro-furan hydrate sediments were carried out in our laboratory to check the theory. By comparison, the theoretical, numerical and experimental results on the evolution of dissociation fronts and temperature in the sediment are found to be in good agreement.

Crystal structure of mixed sodium-potassium paradodecatungstate 6-hydrate

The crystal structure of K7Na3[H2W12O42]3 . 6H(2)O was determined by X-ray crystallography,and refined to R=0.0864 based on 7024 observed reflections (I>2 sigma(I)). The crystallographic parameters are a=11.755(2), b=13.0493(3), c=16.289(3) Angstrom; alpha=77.13(3)degrees, beta=82.92(3)degrees, gamma=89.65(3)degrees, triclinic, space group, P (1) over bar, V=2416.7(8) Angstrom(3), Z=2, M-r=3330.98, D-cal=4.578Mg/m(3), F(000)=2904; mu (MoK alpha)=29.170mm(-1), T=293K. Two independent polyanions are centered respectively at 1,1,1/2 and 1/2, 1/2, 0, approximately perpendicular to each other with dihedral angle between the equatorial planes of the molecules at 96 degrees. K+ and Na+ respectively occupy the clefts of the two discrete polyanions.