According to Equations (8) and (9), the key parameters determining the migration velocity of hydrated bubble are bubble equivalent radius , hydrate shell thickness and drag coefficient , while the key parameters determining the migration velocity of clean bubble are equivalent radius and drag coefficient . Since these key parameters are affected by temperature and pressure changes, mass transfer, and hydrate phase transition during the bubble migration process, the precise characterization of the key parameters in different bubble migration stages is the basis for accurately calculating the bubble migration velocity.
3.1. Dynamic growth thickness of hydrate shell
When bubble enters the hydrate formation area, a thin hydrate shell will rapidly form on its surface, and the thickness of the hydrate shell is usually called the initial thickness. Shi et al. [
19] found in their experiments that hydrate nucleates on the surface of bubble, and then rapidly covers the whole bubble through lateral growth. Experimental statistics show that the formation time of the initial hydrate shell is between 10 and 25 s. Determining the initial hydrate shell thickness is the basis of establishing the hydrate shell thickness prediction model. Li et al. [
20] measured the initial thickness of hydrate shell under different undercooling degrees. The results show that when the undercooling degree is greater than 1.0 K, the initial thickness of hydrate shell is inversely proportional to the undercooling degree.
where,
is the initial thickness of hydrate shell, m.
is regression coefficient, m·K.
is the degree of undercooling, K. According to the experimental data of Li et al.,
.
Lee et al. [
21] observed the hydrate shell growing on the surface of water droplets in a gas-dominated system, and found that the hydrate shell showed inward growth phenomenon. Li et al. [
22] experimentally studied the growth process of hydrate film on the surface of water droplets suspended in the oil phase, and also found the inward growth phenomenon of hydrate shell. Liu et al. [
12] observed the inward growth phenomenon and local slight bulge of hydrate shell on the surface of suspended bubble in the aqueous phase dominated system. These studies indicate that gas-water mass transfer determines the growth direction and thickness variation of hydrate shell. During the dynamic growth of hydrate shell, the changes of temperature and pressure will lead to the formation of micro-cracks in its interior [
22]. Water penetrates into the hydrate shell under the action of capillary force, while gas diffuses outward through the hydrate shell. As shown in
Figure 3, water penetrates into the gas-side hydrate formation layer through the micro-cracks in the hydrate shell. The water molecules infiltrated into the hydrate shell will combine with the gas molecules diffused outward to form hydrate, which makes the internal structure of the hydrate shell compact. When the gas molecules enter the water-side hydrate formation layer by diffusion, they will first dissolve into the liquid phase. When the concentration of liquid gas reaches saturation, the excess gas molecules will accelerate the growth of hydrate on the water side, and when the concentration of liquid gas is lower than the saturation concentration, the dissolution of gas in the liquid phase will inhibit the growth of hydrate on the water side. Based on the above analysis, the dynamic growth of hydrate shell mainly includes outward growth, inward growth and internal pore renewal.
Based on the above analysis, the reasonable assumptions before establishing the dynamic model of hydrate shell thickness in this study are as follows:
(1) Hydrate shell is a kind of plastic-like material, which has a certain ability to resist damage [
23]. Therefore, the mechanical failure of hydrate shell during bubble migration is not considered.
(2) The hydrate shell has a porous medium-like structure, consisting of hydrate crystals and microscopic pore throats.
After the formation of the initial hydrate shell, the subsequent thickness change depends on the hydrate formation rate inside and outside the hydrate shell. The thickness change of hydrate shell can be expressed as:
where,
is time, s.
and
are hydrate formation rates on the inside and outside of the hydrate shell respectively, kg/s.
The bubble equivalent radius
, hydrate shell thickness
and hydrate shell density
all change with time due to the influence of temperature and pressure change, mass transfer and hydrate shell compact growth. Therefore, the governing equation of hydrate shell thickness can be obtained by differentiating all variables in Equation (11):
When the water molecules on the outside of the hydrate shell permeate to the inside of the hydrate shell through micro-cracks, a large number of gas molecules around it rapidly combine with water to form the hydrate. Therefore, the water penetration rate determines the thickening rate of the inner hydrate shell, and the inward hydrate formation rate can be expressed as:
where,
is the hydration number, dimensionless.
is the molar mass of gas, kg/mol.
is the molar mass of water, kg/mol.
is the density of water, kg/m
3.
is the permeation rate of water through hydrate shell, m
3/s.
According to the model proposed by Mori et al., the total mass transfer rate of water penetration can be expressed as follows [
24]:
where,
is the gas-water interfacial tension, N/m.
is the contact angle of capillary on the water side, rad.
is the capillary radius, m.
is the pressure difference between the inside and outside of the hydrate shell, Pa.
is the ability of water molecules to pass through micro-cracks, m
3, which depends on the number and size of micro-cracks in the hydrate shell:
where,
is the number of micro-cracks per unit area in the hydrate shell, 1/m
2.
is the tortuosity of the micro-cracks, dimensionless.
On the outside of the hydrate shell, the formation rate of hydrate is mainly controlled by the mass transfer and dissolution rate of gas molecules. Therefore, the outer formation rate of hydrate shell can be expressed as:
where,
is the mass transfer rate of inner gas diffusion through the hydrate shell, m
3/s.
is the dissolution rate of gas in the liquid phase, m
3/s.
The mass transfer rate of bubble diffusion can be obtained by solving the steady-state diffusion equation. The diffusion equation adopted in this study is [
25]:
where,
is the gas concentration, m³/ m³.
is the gas diffusion coefficient inside the hydrate shell, m
2/s. The diffusion coefficient
inside the hydrate shell reflects the diffusivity of the gas along the concentration gradient. Ogasawara et al. [
26] obtained that the gas diffusion coefficient inside the hydrate is about 10
-11~10
-12 m
2/s on the basis of experimental research.
In this study, the boundary conditions corresponding to the diffusion equation are:
where,
is the gas concentration inside the hydrate shell, m³/m³.
is the gas concentration outside the hydrate shell, m³/m³.
According to the boundary conditions of Equation (18), the analytical formula of Equation (17) is obtained as follow:
According to equation (19), the gas concentration gradient at position
is:
The mass transfer rate of inner gas diffusion through the hydrate shell is:
The dissolution rate of gas in liquid phase is closely related to the gas concentration difference and mass transfer coefficient at the interface between hydrate shell and liquid phase. In addition, the rate of gas dissolution in the liquid phase also depends on the bubble surface area. The gas dissolution rate at the hydrate shell-liquid interface can be expressed as follow [
27]:
where,
is the gas concentration at the hydrate shell-liquid interface, m³/m³.
is the gas concentration in the liquid phase, m³/m³.
is the mass transfer coefficient between hydrate shell and liquid phase, m/s. The mass transfer coefficient determines the dissolution rate of gas in liquid phase. Rehder et al. [
28] showed that the existence of hydrate shells would increase the mass transfer resistance of gas dissolution and reduce the mass transfer coefficient. The formation of the hydrate shell leads to the transition from the original mass transfer across the gas-liquid interface to the mass transfer across the solid hydrate shell, and the mass transfer coefficient of gas in the solid phase is significantly lower than that in the liquid and gas phases. In order to accurately characterize the effect of the dissolution rate of gas mass transfer across the hydrate shell on the thickness of the hydrate shell, error analysis and optimization of the typical mass transfer model of bubble dissolution in
Table 1 should be carried out by using experimental data. Rehder et al. [
28] experimentally studied the variation law of the equivalent radius of methane bubbles released in the water depth range from 400 m to 1500 m with the bubble migration time. The experimental data were collected and recorded by ROV (Remote Operated Vehicle) observation. The data are of high practical value and have a strong reference significance for the establishment and verification of bubble migration model. Therefore, in this study, error analysis and optimization of the typical mass transfer model of bubble dissolution were carried out based on the experimental data of bubble equivalent radius variation with migration time in hydrate shell formation segment obtained by Rehder et al., which released methane bubbles at a depth of 1098.0 m.
Figure 4 shows the comparison between the calculated results of different typical mass transfer models of bubble dissolution and the experimental data. In this experiment, the equivalent radius of the hydration bubble was recorded by ROV several times from 180 s to 470 s after bubble release. The Clift model, Levich model and Acrivos model all underestimate the gas mass transfer coefficient across the hydrate shell. Compared with the Rehder et al. experimental data, the maximum errors of the models are 21.26%, 17.35% and 23.61% respectively. The Oellrich model, Leclair model, Johnson model and Winnikow model all overestimate the gas mass transfer coefficient across the hydrate shell. Compared with the Rehder et al. experimental data, the maximum error of these models are 22.09%, 68.53%, 28.65% and 43.11% respectively. Based on the above analysis, the existing models can not accurately describe the gas dissolution mass transfer behavior of hydrated bubble. Among them, the average error of the Levich model is the smallest, because the situation that the gas-liquid interface is an immovable interface is considered in the modeling process. The reason for the error of this model is that the influence of the flow field around the bubble on the mass transfer coefficient is not considered. Therefore, a new mass transfer coefficient correlation model is obtained by considering the introduction of Reynolds number to modify the Levich model. The coefficients in the new model are regressed according to the experimental data obtained by Rehder et al.
Error analysis of the new mass transfer coefficient model was carried out using experimental data obtained by Rehder et al. [
28] releasing methane bubbles at water depth of 1209.6 m and 1511.4 m. In these two experiments, the equivalent radius of the hydrated bubbles was observed and recorded respectively during the 140 s to 900 s and the 80 s to 1100 s after the bubbles were released.
Figure 5(a) and
Figure 5(b) show the comparison between the calculated results of the new mass transfer coefficient model for bubble dissolution and the experimental data. The average error is 5.41% and 6.92% respectively, which indicates that the new mass transfer coefficient model of bubble dissolution can accurately characterize the mass transfer behavior of gas across hydrate shell.
The bidirectional mass transfer of gas and water across the hydrate shell is also accompanied by the renewal of pores in the hydrate shell. According to the relationship between the gas and water consumption during the formation of hydrate, we can obtain:
where,
and
are pore radius before and after pore renewal respectively, m.
is the gas consumption, mol. The variation of pore radius in hydrate shell with time can be obtained from equation (24):
where,
is the gas consumption rate in the process of pore renewal, mol/s. The difference between the gas concentration in the hydrate shell near the gas phase and the gas concentration in the hydrate shell near the liquid phase represents the speed of this consumption rate, which can be expressed as:
3.3. Drag coefficient during bubble migration
In the research on resistance coefficient of bubble migration, the existing models are mainly established by correlating with dimensionless numbers such as Reynolds number and Morton number, and the coefficients in the correlation model are obtained by fitting a large number of experimental data. The drag coefficient model of the clean bubble migration section is relatively mature. Since this paper mainly studies the migration of bubble in non-Newtonian fluid in deepwater wellbore annulus, the drag coefficient model established by Rodrigue et al. [
36] based on the experimental data of bubble migration in non-Newtonian fluid is adopted.
where,
is the fluidity index, dimensionless.
Since the current research on the drag coefficient in the migration section of hydrated bubble is not mature, this study selects the drag coefficient model suitable for the migration of hydrated bubble by comparing the previous models with experimental data. As the applicable conditions of each model are different, the drag coefficient model which is widely used to describe bubble migration is selected for comparative analysis with the experimental data obtained during the previous research of our team [
37]. By comparing the agreement between the calculated results of each model and the experimental data, the drag coefficient model suitable for the hydrated bubble migration section in non-Newtonian fluid is optimized. The typical drag coefficient model to describe bubble migration is shown in
Table 2.
As shown in
Figure 6(a) and
Figure 6(b), the Bigalke model has a small difference with the experimental value at
, the Tomiyama model has a high coincidence with the experimental value at
, and the Bozzano model has a high coincidence with the experimental value at
. The average error of these three models in the above interval is less than 10.0%. Since the drag coefficient calculation model is usually selected according to the Reynolds number of bubble migration, the relationship between Reynolds number and drag coefficient in the process of hydrated bubble migration obtained from previous experiments [
37] is used in this study to divide the applicable range of Bigalke model, Tomiyama model and Bozzano model.
As shown in
Figure 7, when
, the drag coefficient value is roughly between 0.5 and 0.95, and the Bigalke model has good adaptability. When
, the drag coefficient is roughly between 0.95 and 1.5, and the Bozzano model has good adaptability. When
, the drag coefficient is greater than 1.5, and the Tomiyama model has good adaptability.
where,
is the Eotvos number, dimensionless,
.
is the bubble equivalent diameter, m.
is the surface tension of drilling fluid, N/m.
is Morton number, dimensionless,
.
is a Weber number, dimensionless,
.