Chemical Engineering Science 56 (2001) 4715–4724

www.elsevier.com/locate/ces

Measuring and modelling the rate of decomposition of gas hydrates

formed from mixtures of methane and ethane
Matthew A. Clarke, P. Raj Bishnoi ∗
Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Drive NW,
Calgary, Alberta, Canada T2N 1N4

Received 15 December 2000; received in revised form 9 March 2001; accepted 27 March 2001

Abstract
The rate of decomposition of gas hydrates formed from mixtures of methane and ethane was measured in a semi-batch stirred-tank
reactor. The experimental apparatus was the same as that used by Clarke and Bishnoi (Chem. Eng. Sci. 55 (2000) 4869; Can.
J. Chem. Eng. (2000) accepted for publication) to measure the kinetics of decomposition of hydrates formed from pure ethane
and methane. Experiments were conducted with methane=ethane mixtures ranging from 25% methane to 75% methane and at
temperatures and pressures between 274 and 278 K and 6.39 to 14:88 bar, respectively. The model of Clarke and Bishnoi was
extended to hydrates that are formed from gas mixtures. For hydrates that were known to form structure I, no new parameters were
needed and the model was found to accurately predict the data. For the structure II hydrates, it was assumed that the rate constant
of ethane was independent of structure because ethane only occupies the large cavities. The intrinsic rate constant and activation
energy for methane in structure II were determined to be 8:06 × 103 mol=m2 Pa s and 77:33 kJ=mol, respectively. ? 2001 Elsevier
Science Ltd. All rights reserved.

Keywords: Gas hydrates; Kinetics; Decomposition; Crystallisation

1. Introduction The discovery of gas hydrates is attributed to Sir

Natural gas hydrates belong to a class of solids
known as clathrates. They are non-stoichiometric crys-
talline compounds that occur when hydrogen-bonded
water molecules form cavities that can be occupied by a
guest molecule. Molecules that can =t in the cavities in-
clude light hydrocarbons, CO2 , H2 S, argon, krypton and
xenon. In the absence of a guest molecule, the cavity is
thermodynamically unstable. Depending upon the guest
molecules and the conditions of formation, one of four
structures may form; structure I, structure II, structure
H, and a new, currently unnamed, structure (Konstantin,
Uchadin, & Ripmeester, 1999). Subramanian, Kini, Dec,
and Sloan (2000) observed that hydrates formed from
mixtures of methane and ethane can form either struc-
ture I or structure II, depending upon the temperature,
pressure and gas-phase composition.
∗ Corresponding author. Tel.: +1-403-220-6695; fax: +1-403-284-
4852.
E-mail address: bishnoi@ucalgary.ca (P. R. Bishnoi).
Humphry Davy, who =rst noticed them in 1810 (Davy,
1811). Hammerschmidt (1934) discovered that hydrates
block natural gas pipelines. Since then, hydrates have
been discovered in large reservoirs occurring in per-
mafrost areas and under the oceans. It is believed that,
worldwide, the total amount of carbon in hydrate form is
twice that of all conventional reserve (coal, oil, natural
gas) combined (Suess, Bohrmann, Greinert, & Lausch,
1999). For this reason, research in the kinetics of gas
hydrate formation and decomposition has been receiving
increasing attention.
The intrinsic kinetics of hydrate formation were =rst
measured by Vysniauskus and Bishnoi (1983, 1985). En-
glezos, Dholabhai, Kalogerakis, and Bishnoi (1987a,b)
recognised that hydrate formation was a crystallisation
process and incorporated the population balance to ac-
count for the total solid hydrate surface area available for
reaction. Englezos et al. (1987b) extended their model
on the kinetics of hydrate formation of pure components
to the formation from gas mixtures. In their approach,
no new adjustable parameters were needed to model the

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 1 3 5 - X
4716 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724
intrinsic rate of gas hydrates formation from gas mixtures.
Skovborg and Rasmussen (1994) simpli=ed the model of
Englezos et al. (1987a,b) by assuming that mass transfer
at the gas=liquid interface was the limiting step in hydrate
growth. Teng, Kinoshita, and Masutani (1995) developed
a kinetic model of hydrate formation on a droplet of CO2
in water at high pressure and low temperature. Kvamme
(1996) proposed a new kinetic model based on the theory
that the initial formation of hydrate takes place towards
the gas side of the interface. Herri, Gruy, Pic, and Cournil
(1999) proposed a model for methane hydrate crystalli-
sation that couples mass transfer at the gas=liquid inter-
face with the population balance to describe the overall
rate of methane hydrate formation.
The intrinsic kinetics of gas hydrate decomposition
has been studied by Kim, Bishnoi, Heidemann and Rizvi
(1987) and then by Clarke and Bishnoi (2000a,b, 2001).
The mathematical model of Clarke and Bishnoi (2000a,b,
2001) is based upon the work of Kim et al. (1987), with
the addition of the population balance to account for
the particle size distribution. Clarke and Bishnoi deter-
mined the intrinsic rate of ethane hydrate decomposition
(2000a) and methane hydrate decomposition (2001). In
their work, the particle size distribution was measured
with an in-line particle size analyser.
In the current study, a new mathematical model is de-
veloped to determine the intrinsic rate of decomposition
of gas hydrates that are formed from gas mixtures. Ex-
periments with gas mixtures of methane and ethane are
used to verify the new model.
1.1. Experimental apparatus and procedure
The equipment used in the current study is the same as
that used by Clarke and Bishnoi (2000a, 2001) to study
the intrinsic kinetics of gas hydrate decomposition of pure
methane and ethane. However, certain provisions had to
be made to study the gas mixtures. A special sampling
valve was designed to sample the reactor gas phase. The
valve is designed to have zero dead volume. It is possible
to completely purge the valve of the old sample, prior to
taking a new sample. The volume of the sample that is
withdrawn from the reactor is so small that the pressure
does not change noticeably. This implies that the pres-
sure change in the reactor is less than what the pressure
transducer can measure (approximately 5 kPa).
The procedure for the current study can be divided into
three stages: gas dissolution and hydrate particle growth,
stabilisation and, =nally, hydrate particle decomposition.
During hydrate formation, hydrates are formed at a pres-
sure above the three-phase equilibrium pressure. After
the formation has proceeded for a suJcient time, the
pressure in the reactor is reduced to a pressure approx-
imately 50 kPa above the three-phase equilibrium pres-
sure. At this pressure, the driving force for hydrate growth
is negligible and it is possible to measure the particle size
distribution. This is the stabilisation period. The hydrate
decomposition is initiated by further depressurising the
reactor to a pressure below the three-phase equilibrium
pressure.
Each of the three stages is described in detail else-
where (Clarke & Bishnoi, 2000a). The only diKerence in
the procedure followed in the current study and that fol-
lowed in the previous studies (Clarke & Bishnoi, 2000a,
2001) is with respect to the sampling of the gas phase.
The =rst sample is taken at the start of the decomposition
and a second sample is taken at the end of the decom-
position. Prior to sampling, the sampling valve and the
sampling lines are thoroughly Lushed with Helium. Af-
terwards, the sampling valve is =lled with Helium at a
pressure of 50 kPa less than the experimental decomposi-
tion pressure. This ensures that the volume of reactor gas
that is withdrawn is negligible, compared with the total
volume of the reactor gas phase. The gas-phase sample
is captured by momentarily opening the sample valve.
Once the sample has been collected, it is sent to a gas
chromatograph for analysis.
2. Theory
The decomposition of a hydrate particle from a mixture
is envisioned to consist of the same two steps as those
involved in the decomposition of a hydrate that is formed
from a single gas (Clarke & Bishnoi, 2000a, 2001). The
steps are destruction of the clathrate host lattice at the
surface of a particle followed by desorption of the guest
molecule from the surface of a particle. A detailed dis-
cussion of the reaction mechanism is given by Clarke and
Bishnoi (2000a). For modelling this process, it is postu-
lated that the rate of decomposition of a component is not
aKected by the presence of the other components. There-
fore, the total rate of decomposition is equal to the sum
of the decomposition rates of the individual species:

 
dn  
dnH
= = −Ap Kdj (feq − fgV )j
dt p dt j
j j
(j = 1; NH); (1)
where
NH
nH = nj ; (2)
j=1
with nH being the number of moles of gas remaining in the
hydrate during the decomposition. The term (feq − fgV )j
represents the driving force for component j and Kdj is
the intrinsic rate constant for decomposition of compo-
nent j. The rate constants used in Eq. (1) are the rate
constants for the pure components, in the same hydrate
structure as the hydrate formed from the gas mixture.
For methane=ethane mixtures that are known to form
 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724 4717

structure I hydrates, the rate constants that are used are The linear growth rate is obtained starting from Eq. (1)
those found by Clarke and Bishnoi (2000a, 2001) for
 
dnH  
the decomposition of pure methane and ethane. The term = −Ap Kdj feq − fgV j (j = 1; NH );
(feq )j is the equilibrium fugacity of component j in the dt p j
stable hydrate phase for the mixture (sI or sII), at the (1a)
experimental temperature. (fgV )j is the fugacity of com-
ponent j in the gas-phase mixture at the experimental
temperature, pressure and at the gas-phase composition. Ap = s L2 ; (8)
Thus, the eKect of the mixture composition is accounted
for indirectly in the calculation of the fugacities. Vp = V L3 ; (9)
As was done for the case of decomposition of a hy-
drate formed from a single component, the global rate of
reaction may be obtained by integrating Eq. (1) over all Vp V L3
nH = = : (10)
particle sizes, M M

  Eqs. (8) and (10) are substituted into Eq. (1) to give
∞
dnH
Ry (t) = ’(L; t) dL
 
dt p V dL3
0
= −s L2 Kdj (feq − fgV )j ; (11)

 ∞  M dt p j
 2
=− L ’(L; t) dL Kdj (feq − fgV )j

0 3V L2 dL   
j
= −s L2 Kdj feq − fgV j ; (12)
  M dt p j
= − 2 (t) Kdj (feq − fgV )j : (3)


j dL M s 
=G=− Kdj (feq − fgV )j : (13)
dt p 3 v j
The integration in Eq. (3) is only with respect to particle
size, therefore the driving forces are taken out of the
The ratio of the shape factors can be written in terms of
integral.
sphericity by
A material balance on the volume of the reacting mass
gives
2=3
s  6v

 = : (14)
1 dnH v v 
Ry (t) = : (4)
V dt When combined with Eq. (13) the linear growth rate be-
comes
Eqs. (3) and (4) are combined to give
2=3 

 M s 6v
dnH   G=− Kdj (feq − fgV )j : (15)
= − V2 (t) Kdj (feq − fgV )j : (5) 3 v  j
dt j
Case 2: The composition varies only slightly with time.
Clarke and Bishnoi (2000b) derived an analytical expres- In this case, it may be acceptable to take the average of
sion for the second moment for the case of no particle the fugacity diKerences at the beginning and at the end
breakage or agglomeration. The expression for the sec- of the experiment. For this case the solution to Eq. (5)
ond moment in this case is becomes


2 (t) = 00 t 2 G 2 + 210 Gt + 20 : (6)  1 0 23
nH (t) = n0 − V 0 G t + 10 Gt 2 + 20 t
3
There are three possibilities for solving Eq. (5) 
Case 1: The gas-phase composition in the reactor is × Kdj (feq − fgV )j; ave ; (16)
j
assumed to remain constant. Thus, the fugacity diKerence
is constant. Therefore Eq. (5) can be combined with Eq.
2=3 
M s 6v
(6) and integrated to give G=− Kdj (feq − fgV )j; ave : (17)
3 v 

 j
 1 0 23 0 2 0
nH (t) = n0 − V  G t + 1 Gt + 2 t Case 3: The last case is where the composition varies
3 0
 appreciably with time. For this case it is not likely that
× Kdj (feq − fgV )j : (7) there is an analytical solution to the population balance.
j Therefore, the following equations would have to be
4718 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724

solved simultaneously: Table 1

 Average molecular mass of the hydrate formed from gas mixtures
dnH  
= − V2 (t) Kdj (feq (t) − fgV (t))j ; (18) Mixture composition Molecular mass
dt j (kg=mol)

d0 25% CH4 =75% C 2 H6 0.1270

= 0; (19) 65% CH4 =35% C 2 H6 0.1267
dt 72% CH4 =28% C 2 H6 0.1260
75% CH4 =25% C 2 H6 0.1258
d1
= G(t)0 ; (20)
dt
d2
= 2G(t)1 ; (21) model of van der Waals and Platteuw (1959). From their
dt
model, the ratio of the number of molecules of species k

2=3  in cavity i to the number of water molecules is
M s 6v
G(t) = − Kdj (feq (t) − fgV (t))j : Nk; i
3 v  j = yk; i "i ; (23)
Nw
(22) where
The use of Eqs. (18) – (22) would require simultaneous Cki fi
yk; i = : (24)
(P; T; yi ) measurements. This was not possible with the 1 + Cki fi
current apparatus. The fugacity, fi , is the fugacity of the hydrate former at
equilibrium and Cki is the Langmuir constant.
The Langmuir constants in Eq. (24) are found by using
3. Results and discussion an intermolecular potential function. Traditionally, the
Kihara potential is used with gas hydrates.
Four methane=ethane mixtures were chosen to test When the values of a; % and & that are determined from
the proposed model. The compositions that were chosen pure methane and pure ethane are applied to mixtures of
were 25% CH4 =75% C2 H6 ; 65% CH4 =35% C2 H6 ; 72% the two, thermodynamics predicts that structure I hydrates
CH4 =28% C2 H6 , and 75% CH4 =25% C2 H6 . The =rst two will form over the entire composition range. However, it
compositions are known to form structure I hydrates, has recently been experimentally observed (Subramanian
while the second two compositions have recently been et al., 2000) that mixtures of methane and ethane can form
shown to form structure II hydrates (Subramanian et structure II hydrates in the range of 72–99.3% methane, at
al., 2000). Structure II hydrates were found to form at 274:2 K. For this reason, it was necessary to regress new
methane compositions between 71% and 99.3%. The Kihara potential parameters that will predict the observed
reason for small amounts of ethane causing structure II structural transition. The values of these parameters are
to be more stable is believed (Subramanian et al., 2000) reported by Clarke (2000).
to be due to competition between CH4 and C2 H6 to oc- By knowing the fractional occupancy, and the number
cupy the large cage in the structure I lattice. Methane’s of water molecules in a unit cell, the molar mass may be
tendency to occupy the small cages and ethane’s ability written as
to =ll only the large cages causes structure II to be stable  

  Nk; i
for certain compositions. M = N w Mw + Mk : (25)
k i
NW
3.1. Determination of the density and molar mass The molecular mass of the hydrate formed from each
of a hydrate formed from a gas mixture mixture that was used in this study is summarised in
Table 1. The values in Table 1 are averaged over the range
In order to describe the kinetics of gas hydrate decom- of temperatures at which the experiments were conducted.
position from gas mixtures, it is necessary to know the The molecular mass does not change appreciably over
density and the molar mass of the hydrate. The molar the temperature range.
mass and density of the hydrate depend upon the degree With the values for the fractional =lling of each cavity
of =lling of each cavity by each species. By knowing the type, the hydrate density may be calculated based upon
fractional occupancy of each cavity, by each species, it is a unit cell. Based upon a single unit cell, the hydrate
possible to determine both the molar mass and the den- density may be written as (Sloan, 1997)
sity of the hydrate.  
The equilibrium fractional occupancy of each cavity NW =NA [MW + Cj=1 Ni=1 yij "i Mj ]
= : (26)
may be calculated from the statistical thermodynamic Vcell
 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724 4719

Table 2 three-phase equilibrium pressure. This occurs at approx-

Average density of the hydrate formed from gas mixtures
Mixture composition
25% CH4 =75% C 2 H6
65% CH4 =35% C 2 H6
72% CH4 =28% C 2 H6
75% CH4 =25% C 2 H6
Since sI and sII are cubic structures, the cell volume,
Vcell , may be calculated by cubing the cell length. The cell
lengths are 12 A R for sI and 17:3 A
R for sII. The calculated
values of hydrate density formed from each mixture that
was used in the study are tabulated in Table 2. Like the
molecular mass, the density does not change greatly with
temperature.
3.2. Mass balance
Fig. 1 shows the data for a typical experiment, in-
cluding dissolution, formation, stabilisation and decom-
position. During the dissolution stage, A in Fig. 1, gas
is being absorbed into water. At approximately 1100 s,
there is an abrupt change in the slope of the curve. This
point corresponds to the appearance of hydrate nuclei.
The hydrate growth phase is labelled B. After the hy-
drates have been allowed to grow for a suJcient time,
the supply gas is stopped and the pressure in the reac-
tor is reduced to a pressure of about 0:5 bar above the
imately 1500 s in Fig. 1. During the stabilisation phase,
Density C, it is assumed that because the pressure is very close
(kg=m3 ) to equilibrium, the driving force for hydrate growth is
negligible and thus, the size of the hydrate particles stays
975.41
974.79 constant. At this point, the size distribution of the hydrate
968.01 particles is measured. The size distribution for a typical
966.18 sample is shown in Fig. 2. The moles of hydrate former
in the hydrate phase at this point gives n0 . The value of
n0 obtained from particle size analyser, which is calcu-
lated by knowing the total solids volume, is 0:01450 mol
and the value from the gas-phase measurements, which
is based upon the pressure–temperature measurements,
is 0:01181 mol. In the experiment shown in Fig. 1, it is
seen that the value of n0 obtained from the particle size
analysis is larger than the value obtained from the gas
pressure=temperature measurements. However, not all the
experiments gave n0 from the particle size analysis be-
ing greater than that from the gas-phase analysis. As was
postulated by Clarke and Bishnoi (2000a,b), this diKer-
ence may be due to the non-sphericity of the particles as
well as in the extrapolation of the particle size distribu-
tion to diameters less than 5 m. A detailed discussion
on the extrapolation process is given in Clarke and Bish-
noi (2000a). At t = 1900 s in Fig. 1, the decomposition
process is initiated by further reducing the pressure to
a value below the three-phase equilibrium pressure. The
decomposition section is labelled D in Fig. 1.
Clarke (2000) established that heat and mass transfer
eKects are eliminated with the current equipment and thus,
the rate constants that are obtained are the intrinsic rate
constants.

Fig. 1. Moles of gas consumed during formation and remaining in the hydrate phase during decomposition for 25% CH4 =75% C2 H6 at 275:15 K,
6.88 bar.
4720 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724

Fig. 2. Particle size analysis for 25% CH4 =75% C2 H6 at 275:15 K, 6.88 bar.

Table 3 pressures from 6 up to 16 bars. Fig. 3 shows the results for

Gas-phase analysis the decomposition section of a typical experiment. The
Cylinder CH4 Initial CH4 Final CH4 experimental data shown in Fig. 3 is from a gas that is
composition composition composition known to form structure I hydrates. As was shown in the
(mol%) (mol%) (mol%) previous section, the results from the gas-phase analysis
25% 24.395 24.398 suggest that it is possible to assume that the composition
65% 65.247 64.566 of the gas is constant throughout the experiment.
72% 72.594 72.998 For mixtures of methane and ethane that are known to
75% 74.606 74.396 form structure I hydrates, no new adjustable parameters
are needed. In the proposed model, the intrinsic rate con-
stants that are used are those that were determined from
3.3. Veri7cation of constant composition assumption the experiments with the pure methane and pure ethane.
The composition is implicitly accounted for in the deter-
From the theory section, it is seen that the solution of mination of the equilibrium fugacity, the density and the
Eq. (5) depends upon whether or not the composition in molecular mass of the hydrate. All fugacities were calcu-
the gas-phase remains constant. Preliminary experiments lated using the Trebble–Bishnoi equation of state (Treb-
were conducted with each of the four gas mixtures to ble & Bishnoi, 1987, 1988). It is seen that there are small
determine whether or not the gas-phase composition re- deviations between the experimental data and the model
mained constant during the decomposition. Table 3 shows predictions. These deviations can be attributed to the un-
the gas-phase composition for each mixture at the begin- certainties in the intrinsic rate constant and activation en-
ning and at the end of the decomposition section. The ergies for the pure methane and ethane and to the fact
compositions listed in Table 3 are the mole fractions of that the rates of decomposition may, in fact, not be ad-
methane, the remainder is ethane. ditive. The diKerence between the experimental data and
Table 3 clearly shows that, for the methane=ethane sys- the model results is 5:84 × 10−4 mol, or 6.5%, after 600 s.
tem, the assumption of constant gas phase composition This is considered an acceptable error. Fig. 2 shows the
is justi=ed. particle size analysis that was measured before the onset
of decomposition. It is seen that the mean diameter of the
3.4. Experimental results for structure I hydrates hydrate particles is approximately 10 m, which is simi-
lar to that of pure methane and pure ethane. The results
Experiments were conducted with the gas mixtures at for other experiments are qualitatively identical and thus,
temperatures ranging from 274.65 up to 278:15 K, and are not shown.
 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724 4721

Fig. 3. Moles of gas remaining in the hydrate phase during decomposition for 25% CH4 =75% C2 H6 at 275:15 K, 6.88 bar.

The composition of the gaseous mixture has a strong Table 4

inLuence on the rate of hydrate decomposition, as it sig- Intrinsic rate constant of methane hydrate decomposition in structure
II
ni=cantly alters the three-phase equilibrium gas-phase fu-
gacity as well as the experimental gas-phase fugacity. Temperature (K) Rate constant × 1011
(mol=m2 Pa s)

3.5. Experimental results for structure II hydrates 274.65 1.637

275.15 1.644
275.15 1.686
For experiments with the gas mixtures that formed 276.15 1.902
structure II hydrates, 72% methane and 75% methane, in 276.15 1.819
the proposed model it is necessary to use the rate constant 277.15 2.135
for the decomposition of the pure component in a struc- 277.15 2.198
ture II hydrate. However, since pure methane and pure 278.15 2.437
278.15 2.420
ethane both form structure I hydrates, these rate constants
are not available.
If the rate constant for either ethane or methane in struc- or
ture II were available then the other rate constant could be
determined. Because ethane only enters the large cavity Kd0 = 8:06 × 103 mol=m2 Pa s;
in both structure I and structure II, it may be assumed that
the rate constant for ethane decomposition is the same in SE
= 9012:7 K ± 511:82 K
both structures. Methane can enter both cavities in struc- R
tures I and II. Thus, the data from the experiments with or
the structure II hydrates, along with the model, can be SE = 77:33 kJ=mol:
used to determine the intrinsic rate constant of decompo-
sition for methane in structure II hydrates. The activation energy for methane hydrate decomposi-
Table 4 shows the estimated rate constants for methane tion in structure II is seen to be slightly lower than in
hydrate in structure II. As would be expected, it is seen structure I. This indicates that, assuming equal surface ar-
that the rate of methane decomposition from a structure eas and driving forces, structure II methane hydrates will
II hydrate increases as the temperature increases. A plot decompose faster than structure I methane hydrates.
of ln(Kd ) vs: 1=T , Fig. 4, was used to determine the fol- Fig. 5 illustrates how the eKect of hydrate structure on
lowing: the modelling results. The solid line is the model that
results from the structure II study (structure II thermo-
ln(Kd0 ) = 8:99 ± 1:85 dynamics + structure II rate constant) and the dashed line
4722 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724

Fig. 4. Arrhenius plot for methane in structure II.

Fig. 5. EKect of structure and Kd on the rate of decomposition.

 M. A. Clarke, P. R. Bishnoi / Chemical Engineering Science 56 (2001) 4715–4724 4723

is that obtained by assuming the mixture forms a struc- the same in sI and sII and an intrinsic rate constant was
ture I hydrate (structure I thermodynamics + structure regressed for methane in sII hydrates.
I rate constant). The structure II solution corresponds to
a lower equilibrium pressure and thus a lower equilib-
rium fugacity. Since the experimental gas-phase fugacity Notation
is unaKected by the structure, the driving forces for the Ap surface area of a particle, m2
decomposition of a structure I hydrate is larger than for a Cij Langmuir constant of species j in cavity type
structure II hydrate. Hence assuming a structure I hydrate i; 1=Pa,
slightly overestimates the rate of decomposition. equilibrium fugacity, Pa
The structure of the hydrate is accounted for both in the fgV fugacity of the hydrate former in the gas
equilibrium fugacity and in the rate constant for methane. phase, Pa
Fig. 5 illustrates the eKect of accounting for the structure G linear growth rate, m=s
solely through the thermodynamics. In this =gure, the Kd decomposition rate constant, mol=m2 Pa s
curve labelled “sensitivity” is the predictions that arise Kd0 intrinsic decomposition rate constant,
when the pure component rate constants are used in con- mol=m2 Pa s
junction with the structure II thermodynamics (structure L characteristic length, m
II thermodynamics + structure I rate constant). It is seen M molecular mass, kg=mol
that the absolute deviation between the sensitivity curve Nw number of water molecules
and the experimental data is as large as that between nH (t) moles of gas remaining in the hydrate phase
the experimental data and the predictions that arise when during decomposition, mol
the mixture is assumed to form structure I hydrate. Af- n0 moles of gas in the hydrate phase at the start
ter 600 s, the deviation between the sensitivity curve and of decomposition, mol
the experimental data, 0:000738 mol, is as large as that R universal gas constant, 8:314 J=mol K
between the experimental data and the predictions that Ry (t) global rate of reactions, mol=m3 s
arise when the mixture is assumed to form structure I t time, s
hydrate, 0:000753 mol. These diKerences correspond to V volume of reacting mass, m3
11.2% and 12.4%, respectively. This deviation indicates Vp volume of a particle, m3
that it is desirable to take structure into account, both in Vcell volume of cell, m3
the equilibrium fugacity as well as the intrinsic rate con- yij fractional occupancy of species j in cavity
stant of methane, when predicting the decomposition of type i
a hydrate that is formed from a gas mixture.
Greek letters

4. Conclusion SE activation energy, J=mol

m mth moment of the particle size distribution,
Experiments have been performed to study the kinetics mn =m3
of decomposition of gas hydrates that are formed from " number of cavities per water molecule
mixtures of methane and ethane. The model of Clarke  density, kg=m3
and Bishnoi (2000a,b) has been extended to model the v volume shape factor
intrinsic rate of decomposition of hydrates that are formed s surface area shape factor
from mixtures. ’ particle density function, m−4
Experiments were conducted with mixtures of methane sphericity
and ethane, ranging in composition from 25% methane
up to 75% methane. Gas-phase analysis revealed that the
composition of the reactor gas remained constant during Acknowledgements
the decomposition process.
For the two gas mixtures that were known to Funding for this work was provided by the Natural
form sI hydrates (25% CH4 =75% C2 H6 and 65% Sciences and Research Council of Canada (NSERC).
CH4 =35% C2 H6 ), the rate constants that were used were
those obtained from the pure component decomposition. References
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