Modeling Methane Hydrate dissociation X-ray CT data Using a

Heat Transfer Model

Arvind Gupta, E.D. Sloan, Jr.*
Center for Hydrate Research, Colorado School of Mines, Golden, CO, U.S.A

Timothy J. Kneafsey, Liviu Tomutsa, George Moridis

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA, U.S.A

ABSTRACT
An x-ray computed tomography (CT) technique was used to quantify pure methane hydrate dissociation.
In this work, hydrate was formed from granular ice in a cylindrical vessel analogous to pipeline geometry.
A slow depressurization combined with thermal stimulation was applied to dissociate the plug. CT images
were obtained during hydrate dissociation to confirm the radial dissociation of hydrate plug. The position
of the dissociation front was calculated from CT images as a function of time with the plug temperature
maintained above the ice point. Further, a one–dimensional radial heat conduction model was applied to
predict the dissociation front location. The heat transfer model prediction was in good agreement with
data.
Keywords: X-ray computed tomography, CT images, dissociation front, depressurization

NOMENCLATURE EXPERIMENT DESCRIPTION

Ap hydrate particle surface area [m2] The experiment was performed in an X-ray
f fugacity [Pa] transparent 7.6 cm I.D. x 25.4 cm cylindrical
k thermal conductivity [W/m/K] aluminum vessel. First, the vessel was packed
Kd kinetic dissociation reaction constant with sieved ice particles of 250 – 850 µm, with
[1/s2] 40 percent initial porosity (gas phase volume
P pressure [Pa] fraction). Hydrate was formed in the vessel by
r radius [m] melting the ice in the presence of methane at
r1 position of dissociation front [m] pressure exceeding the hydrate stability
t time [s] pressures at the experiment temperature [5]. A
T temperature [oC] pressure transducer was used to measure vessel
∆T driving force [oC] pressure with in accuracy of 0.007 MPa. Four
α thermal diffusivity [m2/s] Type T thermocouples (18 inch long, 1/16 inch
ε porosity diameter, from Omega Engineering) were
ρ density [kg/m3] located radially at known locations from center
λ hydrate heat of dissociation [J/kg] to the edge of the vessel. The system
temperature was controlled by circulating a
SUBSCRIPTS AND SUPERSCRIPTS water/propylene glycol coolant through the PVC
e equilibrium jacket surrounding the vessel. A detailed
G gas phase description of experimental set-up is
H hydrate phase provided elsewhere [6].
o boundary
In this experiment, a modified Siemens
INTRODUCTION Somatom HiQ medical CT scanner was used to
Hydrate plugs are a major problem for the oil btain X-ray CT data. Axial cross sections 1 mm
and gas industry during transportation of oil and thick were obtained by scanning the
gas from offshore. Commonly, a two-sided horizontally-oriented cylindrical sample with an
depressurization technique is used to dissociate x-ray energy of 133 keV and a current of 120
the hydrate plug inside the pipelines [1].Several mA. The CT images were collected throughout
researchers have studied the plug dissociation the hydrate formation and dissociation processes
and observed radial dissociation of hydrate plugs with a minimum time resolution of 2 minutes.
[2, 3, 4]. X-ray attenuation is a function of density
____________________________
*Corresponding author: E-mail: esloan@mines.edu
and atomic number, and here the CT images
indicate the density of the material within a
specific volume of 250µm x 250µm x 1mm.
Thus, density changes due to hydrate formation,
dissociation, and mechanical changes can be
obtained. Each image contains 512 x 512 voxels.
RESULTS
CT images were taken at different time intervals
showing the changes which occurred during
hydrate formation and dissociation. After
formation, the hydrate plug was dissociated
slowly with a combined depressurization and
thermal stimulation technique. CT images were
used to locate the hydrate dissociation front as a
function of time.
HYDRATE FORMATION
Based on gas consumption, 93 % (by mass) of
ice was converted into hydrate over an interval
of 2 days. CT images of 1 mm slices in the
longitudinal direction were taken at different
intervals during hydrate formation. Figure 1
shows the CT images at a one location taken
before and after hydrate formation from granular
ice. Packing heterogeneity is clearly visible.
1 2 Tedge
Touter
Tinner
Tcenter
0.30 0.50 0.70 0.90 1.10 1.30
Density (g/cm3)
Figure 1: CT images of porous ice (1) and
hydrate (2). The outer white outer circle is the
aluminum pressure vessel. The four white
interior spots show the thermocouples inserted
in the vessel.
Comparing Images 1 and 2 in Figure 1 shows a
decrease in density of the center of the sample.
The porosity throughout the sample (except at
the center) slightly decreased upon hydrate
formation. The density decreased in the center
was due to the water moving from the melting
ice towards the hydrate existing closer to the
vessel wall.
HYDRATE DISSOCIATION
Hydrate dissociation was induced by slow
depressurization from 4.78 MPa to 3 MPa
while maintaining the boundary temperature at
6oC. Due to the endothermic nature of the
dissociation process, the center hydrate plug
temperature decreased from 6oC to 1.95oC.
Figure 2 shows the change in dissociation
temperature driving force (or sub cooling). The
temperature driving force is defined as:
∆ T = Te Psystem,measured − Tplug ( ) (1)
The methane hydrate equilibrium temperature at
system pressure was calculated using an in-
house program, CSMGem [7]. When the driving
force was negative, hydrate became unstable and
dissociated into gas and water. There was no ice
formation throughout the dissociation
experiment because the plug temperature was
always above the ice point.
0.2
0.1
Tcenter
T e q m . - T p lu g ( d e g C )
0.0
-0.1
Tinner and Touter
-0.2
Tedge
-0.3
-0.4
-0.5
0 50 100 150 200 250 300
Time (minutes)
Figure 2: Driving force at the four
thermocouple locations (the edge, outer, inner
and at the center of the plug) as a function of
dissociation time.
After about 75 minutes, the temperature driving
force became negative and the system P-T
conditions moved from thermodynamically
stable to unstable. This observation was also
confirmed with CT images showing the
appearance of a less dense phase close to the
vessel’s outer boundary indicating that the
hydrate plug had started to dissociate. After 150
minutes, the temperature at the edge (Tedge)
started to increase (the driving force became
more negative) indicating the hydrate
dissociation front had passed the edge
thermocouple and the front continued to move
inward towards the center of the vessel.
During dissociation, CT images were alternately
taken at two different locations every ∼ 2
minutes. Figure 3 shows the radial dissociation
front moving toward the vessel’s center with
time. In this experiment, heat transfer through
conduction in the radial direction was provided
by coolant circulating around the vessel.
Hydrate close to the vessel boundary dissociated
first. Due to gravity and capillarity, the water
produced from hydrate dissociation drained
inward and down. This observation was
confirmed by Images 4, 5 and 6 in Figure 3. The
density at the plug center increased from 0.3 to
0.9 g/cm3.
From the CT images, approximately, 25 percent
of the plug area was in contact with the vessel,
while the remaining 75 percent had gas contact
as shown in Image 6 of Figure 3. The rate of
heat transfer to the plug depends on the
thickness and surface area of different phases
contacting the plug. This observation was used
while modeling the data. ImageJ® [8], an image
processing program, was used to calculate the
position of dissociation front with time from CT
images. The hydrate dissociation slowed after
the plug lost condensed phase contact with the
boundary. Data were gathered for 250 minutes.

1 2 3

t=0 min t=66 min t=120 min

4 5 6

t=180 min t=204 min t=248 min

0.30 0.50 0.70 0.90 1.10 1.30

Density (g/cm3)

Figure 3: X-ray CT images showing the radial movement of the front during hydrate dissociation induced
by depressurization. Every image contains hydrate, gas (dark area) and water phase (light grey). The outer
white circle represents aluminum pressure vessel.
MATHEMATICAL MODELLING
A single moving boundary radial heat
conduction model was used to predict the
hydrate/gas dissociation front as a function of
time. This model was developed and validated
with experimental data on flow line plugs at the
Colorado School of Mines [2, 3, 7]. For this
work the code was modified to predict the
dissociation front assuming that the gas
completely surrounds the plug.
The schematic diagram of the hydrate
dissociation in the model is presented in Figure
4. The outer circle shows the casing through
which the coolant circulated to supply the heat
in the radial direction. The other two circles
reflect the gas and hydrate phase boundaries.
Heat
Gas
Equation 2 was solved numerically using a finite
element technique [2]. Five input parameters
were used to solve the equation: hydrate
structure (e.g. sI or sII), bath temperature, plug
porosity, vessel inner radius and hydrate plug
temperature. The model was developed for the
constant plug temperature conditions during the
dissociation process.
Figure 5 shows the model prediction of the
dissociation front with time for five constant
plug temperatures (5.2 oC, 4.7 oC, 3.9 oC, 2.9 oC
and 1.9 oC).The dissociation front started from
the vessel radius (3.81 cm) and progressed
towards the center of the plug with time. The
hydrate plug dissociate faster for lower plug
temperature, because heat transfer via
conduction is faster when the temperature
difference is greater. Only the first 300 minutes
data are shown in Figure 5.
3.9

3.8
Heat Hydrate Heat

r1 3.7
D is s o c ia tio n fr o n t ( c m )

o
Tplug = 5.2 C
ro 3.6
Tplug = 4.7oC
`
3.5 Tplug = 3.9oC

Tplug = 2.9oC
3.4
Tplug = 1.9oC
Heat
3.3
Figure 4: Schematic physical configuration.
3.2
The governing equation is based on Fourier’s 0 50 100 150 200 250 300
Law: Time (minutes)

∂TG ⎡ 1 ∂TG 2
∂ TG ⎤ Figure 5: Predicted dissociation front location
= αG ⎢ + ⎥ ( 2) with time for different plug temperatures.
2
∂t ⎢⎣ r ∂r ∂r ⎥⎦
Except for the hydrate plug temperature, the
other input parameters remained constant with
The boundary conditions are as follows: time during dissociation. The experimental data
includes the plug temperature at four different
locations allowing the computation of average
T =T r=r t>0
G o o temperature with time during plug dissociation.
∂T ∂r
-k
G
G
(
= 1−ε ρ ) λ
H H
1
r=r
1
t>0 The model is formulated for the constant plug
∂r ∂t temperature during dissociation [2, 3]. But, in
this work, the plug temperature decreased by
T =T r=r t>0
G H 1 4oC over the 250 minutes time interval.
Therefore, an alternative approach was used to 3.9
predict the position of the front with time for the
variable plug temperature case. Experimental Data
3.8
Model Prediction
The average plug temperature was calculated
3.7
with time using the measured thermal data .To
account for the variable plug temperature, the

D is s o c ia t io n f r o n t ( c m )
position of the front was determined from Figure 3.6
5 by using the constant plug temperature
prediction curve (corresponding to the average 3.5
plug temperature) at a given time. Using this
method, the hydrate dissociation front position is 3.4
predicted with time, as shown by the dashed
lines in Figure 5 and tabulated in Table 1. 3.3

3.2
Time T plug average Front Location 0.0 50.0 100.0 150.0 200.0 250.0
(minutes) (oC) (cm) Time ( minutes)

0.00 6.0 3.81 Figure 6: Comparison between the experiment

data and model prediction of dissociation front
19.44 5.7 3.76 location with time.
38.89 5.2 3.73
1) The rate of heat transfer to the hydrate plug
58.33 4.7 3.69 from various sources such as an external heat
source, the vessel wall and initially from hydrate
101.80 3.9 3.60
plug itself [9].
115.16 3.7 3.57
2) The thermal properties of the plug such as
171.37 2.9 3.48 effective thermal conductivity and heat capacity.
186.98 2.7 3.44
3) Intrinsic kinetics involved in hydrate
247.08 1.9 3.35 dissociation, which means the rate of hydrate
dissociation is a function of thermodynamic
Table 1: Predicted dissociation front location driving force and surface area. Outside the
hydrate stability region, Equation 3 described
The predicted dissociation front is shown to be the hydrate dissociation rate, as developed by
in good agreement with the data in Figure 6. The Kim et al. [10]
solid line represents the model prediction and
symbols show the measured position of
dissociation front for one particular slice.
⎛ dn H ⎞
⎜ ⎟ = K d AP
⎝ dt ⎠ P
( feq − f gV ) (3)
DISCUSSION AND CONCLUSION
In contrast to the above equation, the heat-
To dissociate hydrate, two conditions need to be transfer model assumes instantaneous
fulfilled: 1) the system pressure and temperature dissociation outside the hydrate stability limit
must be outside the thermodynamic hydrate which is relatively faster than the kinetic process.
stabilty conditions and 2) an energy source is
required to supply the heat of hydrate In the present work, the prediction using the
dissociation. Figure 2 showed that for our test, radial heat conduction model was in good
the temperature driving force was small, agreement with the data. Two model limitations
indicating a low rate of energy supply. To and their effects are qualitatively considered.
predict the plug dissociation time, the following Our model is a heat transfer model and no
factors need to be considered while modeling: kinetic dissociation was used. Because of this,
the model should predict faster dissociation
compared to the kinetic dissociation case.
Secondly, a gas layer was assumed to
completely surround the hydrate plug. However,
CT images showed that about 25 % of the plug
surface area was in contact with water phase. As
a result the model predicted slower plug
dissociation because of reduced heat transfer
through gas phase. So, these two competing
effects tend to offset each other.
In future work we plan to quantify the role of
heat transfer and kinetic during dissociation.
Different dissociation experiments will be
performed by varying the driving force (feq-fg)
while keeping the other parameters such as
boundary temperature constant.
ACKNOWLEDGEMENTS
The authors wish to acknowledge the financial
support received from the CSM hydrate
consortium of energy companies.
and Dissociation in a Partially
Saturated Sand, LBNL-56933, Ext.Abs.
[7] Ballard, A.L., Sloan, Jr., E.D., The next
generation of hydrate prediction: I.
Hydrate Standard States and
Incorporation of Spectroscopy, Fluid
Phase Equilibria, 194-197, 371 (2002)
[8] ImageJ, Image Analysis and Processing
in Java, Developed by National
Institutes of Health. See also:
http://rsb.info.nih.gov/ij/.
[9] Peters, D., Mehta, A., Walsh, J., A
Comprehensive Model based upon Facts,
Conjecture , and Field Experience ,
Proceedings of the Fourth International
Conference on Gas Hydrates,
Yokohama, 2002.
[10] Kim, H.C., Bishnoi, P.R., Heidemann,
R.A., Rizvi, S., Kinetics of Methane
Hydrate Decomposition, Chemical
Engineering Science 42, 1645-1653,
1987.

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