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Determination of the Intrinsic Rate of

Ethane Gas Hydrate Decomposition
ARTICLE in CHEMICAL ENGINEERING SCIENCE NOVEMBER 2000
Impact Factor: 2.34 DOI: 10.1016/S0009-2509(00)00137-8

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Chemical Engineering Science 55 (2000) 4869}4883

Determination of the intrinsic rate of ethane gas

hydrate decomposition
Matthew Clarke, P. R. Bishnoi*
Department of Chemical & Petroleum Engineering, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
Received 22 December 1999; accepted 2 May 2000

Abstract
The kinetics of ethane hydrate decomposition was studied using an isothermal/isobaric semibatch stirred-tank reactor. The
experimental set-up and procedure used was similar to that used by Kim, Bishnoi, Heidemann and Rizvi (1987), Chemical Engineering
Science, 42, (1645}1653) with one major modi"cation; the addition of an on-line particle size analyser. The experiments were
conducted at temperatures ranging from 274.15 to 281.15 K and at pressures between 5 and 11 bar. A new mathematical model is
developed to determine the rate constant of decomposition. The model accounts for the distribution of particle sizes in the hydrate
phase when determining the intrinsic rate constant of decomposition. The e!ect of the rate of stirring on the rate constant was also
investigated to establish the regime where mass and heat transfer e!ects were negligible. The data were then obtained to determine the
intrinsic rate constant. It was found that the activation energy for ethane hydrate decomposition is 104 kJ/mol and the intrinsic rate
constant of decomposition is 2.56;10 mol/m Pa s.  2000 Elsevier Science Ltd. All rights reserved.
Keywords: Gas hydrates; Kinetics; Crystallisation; Particulate; Population balance

1. Introduction
Gas hydrates constitute a class of solids in which small
molecules occupy almost spherical holes in ice-like lattices made up of hydrogen-bonded water molecules. This
class of solids is known as clathrates. Technically speaking, clathrate compounds are characterised by the structural combinations of two substances which remain
associated not through strong attractive forces, but because strong mutual binding of the molecules of one sort
makes possible the "rm enclosure of the other. The hydrate forming gases include light alkanes, carbon dioxide,
hydrogen sulphide, nitrogen and oxygen. Gas hydrates
can exist in one of the four structures: structure I and
structure II (Claussen, 1951; von Stackelberg & MuK ller,
1954; Je!ery & McMullan, 1967), structure H (Ripmeester, Ratcli!e & Tse, 1998) and a new, as of yet unnamed
structure (Konstantin, Uchadin & Ripmeester, 1999).
Ethane is known to form structure I hydrates.
Gas hydrates have signi"cant importance in the petroleum industry. Traditionally, for the transportation of oil
* Corresponding author. Tel.: #1-403-2206695; fax: #1-403-2823945.
E-mail address: bishnoi@ucalgary.ca (P. R. Bishnoi).

and gas, the industry has designed pipelines to operate

outside hydrate forming conditions. This has been accomplished by either adding traditional inhibitors such
as glycols and methanol or by dehydration of the
gas/condensate #uids. One major task encountered by
the petroleum industry is to decompose a hydrate plug
formed accidentally or otherwise. Having reliable data
on the intrinsic kinetics of gas hydrate decomposition
could allow for better predictions of the rates of decomposition in hydrate plugs.
On the other hand, in-situ hydrates found in permafrost regions and under the ocean #oor represent a vast,
untapped natural resource. In order to predict gas production rates from hydrate reservoirs, it is necessary to be
able to account for the rate at which hydrates are decomposing.
In view of the importance of gas hydrates to the petroleum industry, the thermodynamics of hydrate formation
has been studied extensively. Experimental data on the
thermodynamics of gas hydrate formation has been obtained for many systems and the computational methods
to predict gas hydrate formation conditions are well
established.
The "rst experimental observation of gas hydrates was
made in 1811 by Sir Humphry Davis. Carson and Katz

0009-2509/00/$ - see front matter  2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 1 3 7 - 8

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M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

(1942) studied the four-phase equilibria of gas mixtures in

the presence of gas hydrates and of hydrocarbon-rich
liquids. The conditions of hydrate formation in liquid
hydrocarbon/water systems was investigated by Ng and
Robinson (1976). Holder, Corbin and Papadopoulos
(1980) investigated the thermodynamics of gas hydrates
containing methane, argon and krypton. Experimental
equilibrium data for ethane hydrate formation in the
presence of single- and mixed-electrolyte solutions of
NaCl, KCl, CaCl and KBr were obtained by Englezos

and Bishnoi (1991). Dholabhai, Englezos, Kalogerakis
and Bishnoi (1991) measured the equilibrium conditions
for methane hydrate formation in mixed aqueous electrolytes. Handa and Stupin (1992) experimentally determined the conditions of methane and propane hydrate
formation in 70 As silica gel pores. Dholabhai, Kalogerakis and Bishnoi (1993a) measured the equilibrium
conditions of propane hydrate formation in aqueous
electrolyte solutions. The conditions of structure H hydrate formation has been studied extensively by Mehta
and Sloan (1993). Dholabhai, Kalogerakis and Bishnoi
(1993b) measured the formation conditions of CO hy
drates in aqueous electrolyte solutions. The equilibrium
conditions of CO /CH mixtures in electrolyte solutions


was investigated by Dholabhai and Bishnoi (1994). The
equilibrium conditions of CO /CH mixtures in the


presence of electrolytes, methanol and ethylene glycol
was investigated by Dholabhai, Parent and Bishnoi
(1997). Olsen, Majumdar and Bishnoi (1999) investigated
the equilibrium conditions for mixtures of CO and N .


Mahadev and Bishnoi (1999) obtained experimental data
for the equilibrium conditions of hydrogen sulphide hydrates in the presence of electrolytes and methanol.
A comprehensive compilation of the experimental data
reported in the literature is made by Sloan (1997).
van der Waals and Platteeuw (1959) used statistical
thermodynamics to derive a model to predict the incipient hydrate formation conditions. Parrish and Prausnitz
(1972) substituted the Kihara Potential model for the
Lennard Jones potential model, in the work of van der
Waals and Platteeuw, and predicted the formation conditions of hydrates from gas mixtures. Holder and John
(1983) use a modi"ed Langmuir constant that accounts
for aspherical interactions between gas molecules and the
hydrate lattice. Englezos and Bishnoi (1988) combined the
model of van der Waals and Platteeuw with the model of
Pitzer to predict the formation conditions of gas hydrates
in aqueous electrolyte solutions. Bishnoi, Gupta, Englezos
and Kalogerakis (1989) developed a computational procedure to perform multi-phase #ash calculations for systems that contain hydrates. Tse and Bishnoi (1993)
presented a methodology for predicting the incipient
equilibrium for carbon dioxide gas hydrates in the presence of electrolytes such as NaCl, KCl and CaCl .

Clarke, Pooladi-Darvish and Bishnoi (1999) modelled
the conditions for hydrate formation in porous media.

Vysniauskus and Bishnoi (1983) pioneered kinetic

studies of gas hydrate formation above the ice point.
Isothermal, isobaric experiments were carried out in
a semi batch stirred tank reactor, using methane and
ethane. Englezos, Dholabhai, Kalogerakis and Bishnoi
(1987) developed a model for hydrate growth, based on
two-"lm theory and crystallisation theory. Kalogerakis,
Jamaluddin and Dholabhai (1993) examined the e!ect of
anionic, cationic and non-ionic surfactants on the kinetics of hydrate formation. Chun and Lee (1996) reported
the kinetics of CO hydrate formation and Malegoankar,

Dholabhai and Bishnoi (1997) studied the hydrate formation kinetics of CH and CO .


While the kinetics of hydrate formation has been
studied for a few systems, relatively little attention has
been paid to gas hydrate decomposition. Ullerich, Selim
and Sloan (1987) described the decomposition of a synthetic core of methane hydrate as a moving boundary
heat transfer problem. Kim, Bishnoi, Heidemann and
Rizvi (1987) developed a model for the intrinsic rate of
gas hydrate decomposition and determined the rate constant from experimental data for methane. Their experimental work consisted of measuring the amount of
methane collected during the hydrate decomposition,
while maintaining a constant temperature and pressure
in a semi-batch stirred-tank reactor. In order to determine the intrinsic rate constant in their model, the initial
particle size was estimated from settling times and Stokes
law and it was assumed that all particles had the same
diameter before decomposition. Jamaluddin et al. (1989)
combined heat transfer with intrinsic kinetics to simulate
the decomposition of a core of methane hydrate. Khairkhah, Pooladi-Darvish, Bishnoi and Collet (1999) discussed a three-mechanism model (two-phase #uid #ow,
kinetics of dissociation and heat transfer) for the performance prediction of gas production from hydrate reservoirs. Masuda, Fujinaga, Naganawa, Fujuta and
Hayashi (1999) presented a numerical model for predicting the #ow behaviour of gas and water with hydrate
dissociation in a porous media and the results were
veri"ed with results from methane gas}hydrate dissociation in berea sandstone cores.
In the current study, the experimental procedure of
Kim et al. (1987) is modi"ed to include an on-line particle
size analyser. A new mathematical model, which can
account for the initial particle size distribution, is developed and used to determine the intrinsic rate constant
and activation energy for ethane hydrate decomposition.

2. Experimental apparatus and procedure

2.1. Apparatus
The experimental apparatus of Kim et al. (1987) was
modi"ed to include an on-line particle size analyser.

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

4871

Fig. 1. Schematic of experimental apparatus.

Preliminary details regarding the experimental apparatus and procedure have been given by Clarke and
Bishnoi (1999). Fig. 1 shows a simpli"ed schematic of the
experimental apparatus. The current set-up consists of an
isothermal, isobaric semi-batch stirred-tank reactor,
a gas supply reservoir for hydrate formation, a collection
reservoir for decomposition and a Galai PSA 2010 particle size analyser.
The slurry of hydrates is circulated through a highpressure micro#ow cell in the analyser by means of a Gilson 303 reciprocating pump at the rate of 25 ml/min. The
high-pressure micro#ow cell was originally designed to
study asphaltene precipitation (Nielsen, Svrcek & Mehrotra, 1994). The slurry, as it #ows out of the reactor and
through the circuit, would gain heat from the ambient
causing the hydrates to decompose. To prevent the thermal decomposition of hydrates, the entire circuit is chilled by circulating cooling glycol from the reactor bath
through a concentric tube cooling arrangement. The hydrate}water slurry #ows through the inner tube and the
cooling glycol through the outer tube.
The temperature and pressure control system was the
same as that used in the studies of Englezos et al. (1987)
and later by Malegoankar et al. (1997). Di!erential pressure transducers were used to measure the pressure in the
reactor and in the supply and collection reservoirs.
Type-T thermocouples were used to measure the temperature in the reactor and in the reservoirs. The temperatures and pressures were recorded using a NationalInstruments AT-MIO-16X data acquisition card.
A data-acquisition program was written to interface with
the card and to calculate the number of moles of the gas
in the hydrate phase at any time during the experiment.

The Trebble}Bishnoi equation of state (Trebble

& Bishnoi, 1987, 1988) was used for all thermodynamic
calculations.
2.2. Procedure
The procedure for a typical experiment is similar to
that followed by Kim et al. (1987). The major change in
the procedure is due to the particle analyser. Essentially,
the experiment can be divided into three stages: hydrate
formation, stabilisation and hydrate decomposition.
2.2.1. Hydrate formation
The hydrate formation procedure is almost identical
to that used by Englezos et al. (1987) and later by
Malegoankar et al. (1997). Prior to beginning the experiment, the reactor is thoroughly cleaned using double
distilled/de-ionised water and the entire system is #ushed
with the experimental gas. Also, prior to the formation
experiment, the volume of the supply reservoir and of the
collection reservoir are determined from the Ruska pump
experiment (Englezos et al., 1987) and, if necessary, the
laser on the particle size analyser is aligned. A syringe is
used to charge the reactor with 310 ml of double-distilled/de-ionised water.
As soon as the water is in thermal equilibrium with the
reactor, it is charged with the experimental gas to a pressure that is higher than the three-phase equilibrium pressure at the experimental temperature, point A in Fig. 2, in
order to form hydrates. Once the temperatures in the
reservoirs and the reactors have stabilised, the data acquisition program is started. Once the data acquisition
program has determined the moles of gas initially in the

4872

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

Fig. 3. Schematic of mechanism for hydrate decomposition.

Fig. 2. Experimental process path.

3. Development of a new mathematical model

system, the stirrer is started. The number of moles consumed at any time during the formation experiment is
simply the number of moles of hydrate former initially in
the gas phase minus the present value. The appearance
of hydrates, often referred to as the turbidity point, is
marked by a sudden change in the transparency of the
solution.
2.2.2. Stabilisation
Once the formation has proceeded for a suitable length
of time, the supply gas #ow to the reactor is terminated.
The reactor is then depressurised to a pressure of about
0.5 bar above the three-phase equilibrium pressure,
point B in Fig. 2. This is accomplished by transferring the
gas to the collection reservoir R3, thus keeping the system closed during the experiment. At this point, the
particle size distribution of the circulating slurry is measured. Since the system pressure is nearly equal to the
equilibrium pressure, the driving force for hydrate
growth will be negligible.
2.2.3. Hydrate decomposition
Once the particle size distribution has been measured,
the #ow of hydrates to the particle size analyser is terminated, to isolate the sampling loop, and the decomposition
is initiated by further depressurising the reactor to a pressure below the three-phase equilibrium pressure. The gas
produced due to the decomposition is collected in reservoir R3 and the temperature and pressure in the reservoir
and in the reactor are recorded. During the entire experiment, the mass is well stirred. At any time during the
decomposition stage of the experiment, the number of
moles remaining in the hydrate phase is
n(t)"n !m(t)#m(0)
(1)
M
The terms n(t) and n actually account for the moles of
M
gas in the hydrate plus that in the liquid phase. However,
since the liquid phase is saturated, the number of moles in
the liquid phase does not change during the experiment.

The envisioned process of a decomposing hydrate

particle is shown schematically in Fig. 3. As the hydrate
decomposes, a cloud of gas surrounds the hydrate particle. This cloud of gas prevents hydrate particles from
agglomerating or breaking during decomposition. Also,
since the hydrate particle is completely surrounded by
the gas phase, and the liquid phase is saturated with the
gas, it is not necessary to account for liquid side resistance to mass transfer when describing hydrate decomposition kinetics.
Hence, the overall driving force for gas hydrate decomposition is the di!erence between the fugacity of the
hydrate former at the surface of the hydrate particle and
the fugacity of the hydrate former in the cloud of gas. The
fugacity at the surface of the particle is the equilibrium
fugacity of the gas at the hydrate surface temperature.
Also, the fugacity of the hydrate former in the gas cloud
is the same as that in the bulk gas. Kim et al. (1987)
proposed a two-step mechanism for gas hydrate decomposition consisting of the following steps:
1. Destruction of the clathrate host lattice at the surface
of a particle.
2. Desorption of the guest molecule from the surface.
With these assumptions, Kim et al. (1987) wrote the rate
of disappearance per particle as


dn
dt

"!K A ( f !f 4),
B N 
E

(2)

1
1
1
" # .
(2a)
K
k
k
B
P
K
The term k is the reaction rate constant (steps 1 and 2)
P
and the term k is the mass transfer coe$cient. Mass
K
transfer e!ects arise as a result of the temperature di!erence between the hydrate surface and the gas cloud
surrounding the hydrate particle and are dependent
upon the rate of heat transfer as well as upon the degree

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

of mixing. Good mixing of the reacting mass can eliminate the temperature di!erence. Thus, 1/k becomes negliK
gible.
The particle surface area for a non-spherical particle
can be written as
n
A "
" .
N
Q
t

(3)

The sphericity, t, is de"ned as `the ratio of the surface

area of a sphere having the same volume as the particle to
the apparent estimated surface area of the particlea
(Mullin, 1997). Mathematically, the sphericity can be
written as



p 6

T
t"
.
(4)

p
Q
In the model of Kim et al. (1987), the particle surface
area was obtained by measuring the settling time and
applying Stoke's law to obtain an average particle diameter. In the present study, the total surface area is
obtained from the measured hydrate particle size distribution.
A global rate of disappearance can be obtained by
integrating Eq. (2) over all particle sizes present:


p
R (t)"! K ( f !f 4) u(, t) d,
W
B

E
t

p
R (t)"! K ( f !f 4)k (t),
E 
W
t B 

(5)

dn
"
dt

(8)

dn
p
"R (t)<"! <K ( f !f 4)k2 (t),
W
B 
E
dt
t

(9)

R (t) d<"R (t)<.

W
W
4
Equations (6) and (8) can be combined to give

LR

L

dn"(n(t)!n )


R
p
<K ( f !f 4) k (t) dt.
(10)
B 
E

t

The second moment can be obtained from the population balance. By assuming that there is no breakage or
agglomeration, the population balance can be written as
"!

*u
*
# (Gu)"0.
*t
*

mathematical formulation. Eq. (11) can be transformed

into a set of ordinary di!erential equations by using
a moment transformation. Eq. (11) is multiplied by
H and integrated with respect to from zero to in"nity:

*u
*
Hd#
(Gu)H d"0.
(12)
*t
*


Eq. (12) can be integrated term by term as follows:



*u

d
dk
H d"
uH d " H ,
(13)
*t
dt
dt



k " uH d.
(14)
H

The second term in Eq. (12) is integrated by parts. The
derivative term only applies to the product Gu. Also,
when integrating Eq. (12), it must be noted that the value
of the particle density function is zero at size equals zero
and size equals in"nity, and that the linear growth rate is
assumed to be independent of size. Therefore,

*

(Gu)H d"G uH"!j H\u d

*


"!jGk .
(15)
H\
After performing the moment transformations, Eq. (11)
becomes

(6)


k (t)" u(, t) d.
(7)


A material balance on the reacting mass volume gives

4873

(11)

It is not always necessary to solve Eq. (11) for the entire

particle size distribution. Often, it is su$cient to just look
at part of the distribution. This greatly simpli"es the

dk
H "jGk .
H\
dt

(16)

The value of j that is chosen depends on what information is required. For example, if it is the volume of
particles that is important, j is chosen as 3. This would
give four di!erential equations. Setting j equal to in"nity
would give the entire distribution.
For the case of hydrate decomposition, the second
moment of the particle size distribution is needed. The
second moment may be obtained from Eq. (16) by writing
the terms for j"0, 2. This gives the following set of
ordinary di!erential equations:
dk
 "0, k (0)"kM ,


dt
dk
 "Gk , k (0)"kM ,
(17)



dt
dk
 "2Gk , k (0)"kM .



dt
The solution to the above set of di!erential equations
has been given by Clarke and Bishnoi (1999). The solution to the moment equations are

      

k
1
0
0

k "kM tG #kM 1
#kM 0 .




k
tG
2Gt
1


(18)

4874

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

The expression for the second moment can be combined with Eq. (10) to give
p
n(t)"n ! K <( f !f 4)( kM Gt
M t B

E  
#kM Gt#kM t).


The linear growth rate is obtained from


dn
&
dt

"!K A ( f !f 4),
B N 
E

N
A "
,
N
Q
< "
,
N
4
o<
o

n " N" 4 .
&
M
M

(19)

as follows:

n
1
g" n(t)" ! n ! K <( f !f 4) kM Gt

M t B

E 3 
#kM Gt#kM t





" (n(t)" ![n !K a(t)]),


M
B
where
(2)
(3)
(20)
(21)

Eqs. (3) and (21) are substituted into Eq. (2) to give






o
d
4
dt
M

"!K
( f !f 4),
(22)
B Q

E
N
3o
 d
4
"!K
( f !f 4),
(23)
B Q

E
M
dt
N
d
K M( f !f 4)


E
Q.
"G"! B
(24)
dt
3o

N
T
The ratio of the shape factors can be written in terms of
sphericity by using Eq. (4):



n 6

Q"
T
.
(25)
t

n
T
T
When combined with Eq. (24) the linear growth rate
becomes



K M( f !f 4) n
6

E
Q
T

G"! B
.
(26)
3o

t n
T
The negative sign in Eq. (26) is due to the fact that the
particle is shrinking.
Eqs. (26) and (19) completely describe the intrinsic rate
of decomposition of gas hydrates of any arbitrary shape,
as long as the surface area is known.
If it is assumed that all particles have the same initial
diameters, the new model reduces to the model of Kim
et al. (1987).
3.1. Determination of the rate constant
The rate constant, K , can be determined by using
B
a least-squares analysis on Eq. (19) along with the experimental data. It is important to note that the only unknown in Eq. (19) is the rate constant. The least squares
problem can be set up by de"ning an objective function

p
a(t)" <( f !f 4)(kM Gt#kM Gt#kM t).

E  


t

(27)

(28)

The rate constant is chosen to minimise the function g,

in Eq. (27). This occurs where the derivative of the function g with respect to K is zero,
B
dg
"0"2 (n(t)" ![n !K a(t)])a(t).
(29)

M
B
dK
B
This can be rearranged to give
(a(t)n(t)" ![a(t)n !K a(t)])"0,

M
B
a(t)n ! a(t)n(t)"
M
 .
K "
B
a(t)

(30)
(31)

4. Results and discussion

4.1. Validation of the particle size analyser
Preliminary experiments were conducted in order to
test the reliability of the on-line particle size analyser.
These experiments consisted of circulating Latex microspheres, of a known diameter, through the sampling loop
and measuring the size distribution with the particle size
analyser. The microspheres were known to be almost
monodisperse, with a mean diameter of 22.40 lm. The
results from the particle size analyser, as seen in Fig. 4,
show a very narrow size distribution. The average diameter was determined to 22.38 lm. This shows that
the modi"ed #ow cell is capable of producing accurate
readings.
4.2. Mass balance
Fig. 5 shows the data for a typical experiment, including dissolution, formation, stabilisation and decomposition. During the dissolution stage, ethane is being
absorbed into water. At approximately 1500 s, there is an
abrupt change in the slope of the curve. This corresponds
to the appearance of hydrate nuclei. After the hydrates
have been allowed to grow for a su$cient time, the
supply gas is stopped and the pressure in the reactor is
reduced to a pressure about 0.5 bar above the threephase equilibrium pressure. This occurs at approximately

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

4875

Fig. 4. Particle size analysis of 22.40 lm calibration spheres.

Fig. 5. Moles of ethane consumed during formation and remaining in the hydrate phase during decomposition.

3000 s in Fig. 5. During the stabilisation phase, it is

assumed that because the pressure is very close to equilibrium, the size of the hydrate particles stays constant.
At this point, the size distribution of the hydrate particles

is measured. The size distribution for a typical sample is

shown in Fig. 6. The moles of hydrate former remaining
in the hydrate phase at this point gives n . At t"3500 s
M
in Fig. 5, the decomposition process is initiated by further

4876

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

Fig. 6. Particle size histogram for ethane hydrates.

reducing the pressure to a value below the three-phase

equilibrium pressure.
The data from the decomposition section of the experiment, along with Eq. (31), are used to calculate K .
B
A commercial software package called Table Curve (Jandel Scienti"c, 1994) was used to solve Eq. (31).

The Galai particle size analyser hardware has been set

to measure particles in the range 5}600 mm. It was observed from the experimental data that the particle sizes
were always below 600 mm. Therefore, it was necessary
to extrapolate the particle size distribution into the range
2r (D(5 lm, where r is the critical radius of a hyA
A
drate nuclei (Englezos et al., 1987). For the experiment
shown in Figs. 5 and 6, the number distribution function,
u, is obtained from the cumulative oversize number distribution function and is seen in Fig. 7. The cumulative
log-normal oversize number distribution function,
Eq. (32) was "tted to the data:



dy
u"! .
dx

(32)

where a, b, c and d are adjustable parameters and are

determined by using Table Curve (Jandel Scienti"c,
1994). From the above function, the number distribution

(33)

From Eq. (33), the number area and volume distributions below 5 lm can be determined as follows:




V

u(x) dx,
(34)
V
V
A"p u(x)x dx,
(35)
V
p V
<"
u(x)x dx.
(36)
6 
V
From the analysis of the cumulative oversize number
distribution, it can be shown that particles below
5 mm constitute 23.43% of the number distribution,
2.27% of the area distribution and 0.10% of the volume
distribution.
Once the complete particle size distribution is known,
it is possible to calculate the number of moles of ethane in
the hydrate phase, n . The value of n that is calculated
M
M
from the data acquisition should be the same as the value
that is calculated from the particle size analysis. For the
experiment shown in Fig. 5, n is found to be 7.463;
M
10\ mol from the temperature and pressure measurements and 7.201;10\ mol from the particle size analysis. This is a di!erence of about 4%. This di!erence
may be attributed to the non-sphericity of the particles

N"

4.3. Extrapolation of the particle size distribution

b
(c!x)
y"a# 1#erf !
2
(2d

is given by

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

4877

Fig. 7. Cumulative number density oversize plot for ethane hydrates.

and to uncertainties in extrapolating the particle size

distribution.
4.4. Elimination of heat and mass transfer ewects
In order to establish that heat and mass transfer resistances around the particles were not signi"cant, experiments were conducted at various stirring rates. Fig. 8
shows that the rate constant is virtually unchanged in
going from 300 to 500 rpm. It is only below 300 rpm that
the rate constant changes. This implies that heat and
mass transfer resistances start to become signi"cant at
lower agitation rates, or that 1/k , from Eq. (2a), becomes
K
large. Thus, subsequent experiments were conducted at
400 rpm, where the measured global rate is actually the
intrinsic rate.
In particulate systems, it may not be possible to eliminate mass transfer resistances for extremely small particles.
Thus, it is necessary to establish that these small particles do not contribute greatly to the experimental
observations.
For an agitated vessel, the Sherwood number can be
calculated from the FroK ssling correlation,
Sh"2#0.6Re Sc,
k
,
Sh"
D

u
Re" ,
l

(37)
(38)
(39)

l
Sc"
.
(40)
D

The case of Sh"2 corresponds to the situation of di!usion away from a sphere in a stagnant #uid. This is
complete mass transfer control.
The appropriate velocity to use in Eq. (39) is the slip
velocity. The slip velocity is usually assumed to be the
free-fall velocity of the particle (Mullin, 1997). According
to Mullin (1997) the free fall velocity can be estimated by
the following equations:
u "0.153g  Do o\ g\ ,
R
Q
(4g*o/3o ,
Q

4500 lm,
'500 lm.
(41)

Eqs. (37)}(41) show that for ethane hydrate, the Sherwood number approaches 2 as the particle diameter
approaches 56 nm. It was found, however, that the contribution of the particles with diameter less than or equal
to 56 nm to the total number of moles of ethane in the
hydrate phase is negligible.
4.5. Reproducibility of results
The reproducibility of the results was established by
conducting the experiment under the same conditions
and comparing the results from each run. Three runs
were done at a temperature of 275.75 K, a pressure of
5.87 bar and a stirring rate of 400 rpm. From the three

4878

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

Fig. 8. E!ect of agitation rate on the rate constant for ethane hydrate decomposition.

experiments, it was found that the rate constants were

5.32;10\, 5.20;10\ and 5.35;10\ mol/m Pa s.
This variation in the values of the rate constant was
considered acceptable and indicates that the experimental procedure yielded precise results.
4.6. Results for all experiments

4.7. Temperature dependence of the intrinsic rate constant

Fig. 13 shows a plot of ln K vs 1/. The plot shows
B
a good linear "t, suggesting the following Arrhenius-type
equation for K :
B

(42)

From Fig. 13, it is seen that the rate constant increases

with temperature and that the activation energy is positive. A plot of ln K vs 1/ was used to calculate
B
ln (KM )"19.36$2.63
B

KM "2.56;10 mol/m Pa s
B
*E
"12511.39 K$727.4 K
R
or

Figs. 9}12 show the experimental results for the decomposition stage of the experiment at four di!erent
temperatures. Table 1 summarises the rate constants for
ethane at each of the conditions. Because heat and mass
transfer resistances have been eliminated, the global rate
constant, from Eq. (2a), is equal to the intrinsic rate
constant. As expected, the rate constant increases with
temperature.

*E
K "KM exp !
.
B
B
R

or

*E"104 kJ/mol.
Since hydrate decomposition is endothermic, it should
be expected that the activation energy is at least as large
as the heat of formation (Smith, 1981). The heat of formation is approximately 80 kJ/mol. A linear Arrhenius plot
is further evidence that heat and mass transfer resistances
have been eliminated.
4.8. Intrinsic versus global kinetics
The pre-exponential term, KM , is an intrinsic rate conB
stant and is independent of the pressure, temperature,
particle geometry and process geometry. The intrinsic
rate of reaction refers only to the rate at which one
chemical species is converted into another. It is completely independent of physical processes such as heat,
mass and momentum transfer. What is measured in the
laboratory is the global rate of reaction, which is the rate
associated with the bulk temperature and pressure.
However, the construction and operating conditions of
laboratory reactors can be chosen to reduce the di!erences

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

4879

Fig. 9. Moles of ethane remaining in the hydrate phase at 1.0 C and 4.87 bar.

Fig. 10. Moles of ethane remaining in the hydrate phase at 2.6 C and 7.88 bar.

between the global and the intrinsic rates so that the

intrinsic rate constant can be extracted from the experimental data. These di!erences can be completely elimi-

nated only if the concentration of a reactant or product is

the same in all points of a reacting mass and if the
concentrations can change only due to reaction.

4880

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

Fig. 11. Moles of ethane remaining in the hydrate phase at 6.0 C and 7.88 bar.

Fig. 12. Moles of ethane remaining in the hydrate phase at 7.5 C and 10.87 bar.

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

4881

Table 1
Rate constants for Ethane Hydrate Decomposition
(K)

Formation pressure (bar)

Decomposition pressure (bar)

K (mol/m Pa s)


274.15
274.15
275.75
275.75
275.75
279.15
280.65

6.87
6.87
8.37
8.37
8.37
12.87
14.87

4.87
4.87
5.87
5.87
5.87
9.12
10.87

3.65436E-12
3.69074E-12
5.32831E-12
5.20260E-12
5.35292E-12
9.18665E-12
1.13846E-11

Fig. 13. Arrhenius plot for ethane hydrate decomposition.

In the current experiments, the heat transfer e!ects are

eliminated by immersing the equipment in a constant
temperature bath and by conducting experiments close to
the equilibrium pressure. The mass transfer e!ects are
eliminated by agitating the solution. Thus, by eliminating
the mass and heat transfer e!ects, it is possible to isolate
the intrinsic kinetics of gas hydrate decomposition.
4.9. Applications
The intrinsic rate equations obtained from laboratory
data can be combined with the equations for heat, mass
and momentum transfer to obtain global rate equations
that are useful for design and simulation. For example, the
intrinsic kinetic equation can be combined with the energy
balance to describe the decomposition of a synthetic core
of gas hydrate (Jamaluddin et al., 1989). Other applications include, but are not limited to, modelling the decomposition of a pipeline plug and prediction of the
production from hydrate reservoirs.

5. Conclusion
An experimental procedure for the determination of the
intrinsic kinetics of gas hydrate decomposition is presented and a new model for the determination of the intrinsic
kinetics of gas hydrate decomposition is developed. The
new experimental technique utilises an on-line particle size
analyser. The mathematical model is based on the work of
Kim et al. (1987) and crystallisation theory. The intrinsic
rate of ethane hydrate decomposition is calculated from
experimental data. It is found that the rate constant of
ethane hydrate decomposition increases with temperature
and that it follows an Arrhenius relationship.

Notation
A
N
D

f
CO

surface area of a particle, m

di!usivity of species A in B, m/s
equilibrium fugacity, Pa

4882

f4
E
g
G
k
k
K
K
B
KM
B

m(t)
M
n(t)
n
M
P
r
A
R
R (t)
W
Re
S
A
Sh
t

u
u
R
<
<
N
z

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

fugacity of the hydrate former in the gas

phase, Pa
acceleration due to gravity, m/s
linear growth rate, m/s
mass transfer coe$cient, m/s
mass transfer coe$cient mol/m Pa s
decomposition rate constant, mol/m Pa s
intrinsic decomposition rate constant,
mol/m Pa s
characteristic length, m
number of moles of hydrate former in the gas
phase at time t, mol
molecular mass, kg/mol
Number of moles remaining in the hydrate
phase during decomposition, mol
Number of moles in the hydrate phase at the
start of decomposition, mol
pressure, Pa
critical radius of a hydrate nuclei, m
universal gas constant, 8.314 J/mol K
global rate of reactions, mol/m s
reynolds number
Schmidt number
Sherwood number
time, s
temperature K
velocity, m/s
terminal velocity, m/s
volume of reacting mass, m
volume of a particle, m
compressibility

Greek Letters
*E
*o

Q
u
g
k
K
l
o
o
Q
t

Activation energy, J/mol

Density di!erence between the solid and
liquid, kg/m
Volume shape factor
Surface area shape factor
Particle density function, m\
Viscosity, Pa s
mth moment of the particle size distribution,
m/m
Kinematic viscosity, m/s
Density, kg/m
Density of the solid, kg/m
Sphericity

Acknowledgements
Funding for this work was provided by Shell
E & P Houston and by the Natural Sciences and Research
Council of Canada (NSERC).

References
Bishnoi, P. R., Gupta, A. K., Englezos, P., & Kalogerakis, N. (1989).
Multiphase equilibrium #ash calculations for systems containing gas
hydrates. Fluid Phase Equilibria, 53, 97}107.
Carson, D. B., & Katz, D. M. (1942). Gas hydrates. rans. Am. Inst. Min.
Metall. Pet. Eng. 146, 150}162.
Chun, M. K., & Lee, H. (1996). Kinetics of formation of carbon dioxide
clathrate hydrates. Korean Journal of Chemical Engineering, 13(6),
620}626.
Clarke, M. A., & Bishnoi, P. R. (1999). Determination of the intrinsic
kinetics of gas hydrate decomposition kinetics using particle size
analysis. Presented at the 3rd international conference on gas hydrates,
Salt Lake City, Utah, July 18}22.
Clarke, M. A., Pooladi-Darvish, M., & Bishnoi, P. R. (1999). A method to
predict equilibrium conditions of gas hydrate formation in
porous media. Industrial Engineering Chemistry Research, 38,
2485}2490.
Claussen, W. F. (1951). A second water structure for inert gas hydrates.
Journal of Chemical Physics, 19, 1425}1432.
Dholabhai, P. D., Englezos, P., Kalogerakis, N., & Bishnoi, P. R. (1991).
Equilibrium conditions for methane hydrate formation in aqueous
mixed electrolyte solutions. Canadian Journal of Chemical Engineering, 69, 800}805.
Dholabhai, P. D., Kalogerakis, N., & Bishnoi, P. R. (1993a). Experimental study on propane hydrate equilibrium conditions in aqueous
electrolyte solutions. Fluid Phase Equilibria, 83, 455}462.
Dholabhai, P. D., Kalogerakis, N., & Bishnoi, P. R. (1993b). Equilibrium
conditions for carbon dioxide hydrate formation in aqueous electrolyte
systems. Journal of Chemical Engineering Data, 38, 650}654.
Dholabhai, P. D., & Bishnoi, P. R. (1994). Hydrate equilibrium conditions in aqueous electrolyte solutions: Mixtures of methane and
carbon dioxide. Journal of Chemical and Engineering Data, 39,
191}194.
Dholabhai, P. D., Parent, J. S., & Bishnoi, P. R. (1997). Equilibrium
conditions of hydrate formation from binary mixtures of methane
and carbon dioxide in the presence of electrolytes. methanol and
ethylene glycol. Fluid Phase Equilibria, 141, 235}246.
Englezos, P., & Bishnoi, P. R. (1991). Experimental study on the
equilibrium ethane hydrate formation conditions in aqueous electrolyte solutions. Industrial and Engineering Chemistry Research, 30,
1655}1659.
Englezos, P., & Bishnoi, P. R. (1988). Prediction of gas hydrate formation conditions in aqueous electrolyte solutions. A.I.Ch.E. Journal,
34, 1718}1721.
Englezos, P., Dholabhai, P., Kalogerakis, N., & Bishnoi, P. R. (1987).
Kinetics of formation of methane and ethane gas hydrates. Chemical
Engineering Science, 42, 2647}2658.
Handa, Y. P., & Stupin, D. (1992). Thermodynamic properties and
dissociation characteristics of methane and propane hydrates in
70-As -radius silica gel pores. Journal of Physical Chemistry, 96,
8599}8603.
Holder, G. D., Corbin, G., & Papadopoulos, K. D. (1980). Thermodynamic and molecular properties of gas hydrates containing methane,
argon and krypton. Industrial and Engineering Chemistry, Fundamentals, 19, 282}286.
Holder, G. D., & John, V. T. (1983). Thermodynamics of multicomponent hydrate forming mixtures. Fluid Phase Equilibria, 14,
353}361.
Jamalludin, A. K. M., Kalogerakis, N., & Bishnoi, P. R. (1989). Modelling of decomposition of a synthetic core of methane gas hydrate by
coupling intrinsic kinetics with heat transfer rates. Can. J. Chem.
Eng., 67, 948}955.
Jandel Scienti"c. Table Curve, 1994.
Je!ery, G. A., & McMullan, R. K. (1967). The clathrate hydrates.
Progress in Inorganic Chemistry, 8, 45}51.

M. Clarke, P. R. Bishnoi / Chemical Engineering Science 55 (2000) 4869}4883

Kalogerakis, N., Jamaluddin, A. K. M., & Dholabhai, P. D. (1993).
E!ect of surfactants on hydrate formation kinetics. In Proceedings
of the 1993 SPE international symposium on oilxeld chemistry, March
2}5, 1989, New Orleans, LA, USA, (p. 375). Richardson, TX: SPE.
Khairkhah, D., Pooladi-Darvish, M., Bishnoi, P. R., & Collet, T. S.
(1999). In Production potential of the Malik xeld Scientixc results from
JAPEX/JNOC/GSC Malik 2L-38 Gas Hydrate Research Well, McKenzie Delta, Northwest Territories, Canada (p. 377). Canada: Canadian Geological Survey.
Kim, H. C., Bishnoi, P. R., Heidemann, R. A., & Rizvi, S. S. H. (1987).
Kinetics of methane hydrate decomposition. Chemical Engineering
Science, 42, 1645}1653.
Konstantin, A., Uchadin, K. A., & Ripmeester, J. A. (1999). A complex
clathrate hydrate structure showing bimodal guest hydration.
Nature, 397, 420}423.
Mahadev, K. N., & Bishnoi, P. R. (1999). Equilibrium conditions for the
hydrogen sul"de hydrate formation in the presence of electrolytes
and methanol. Canadian Journal of Chemical Engineering, 77,
718}722.
Malegoankar, M. B., Dholabhai, P. D., & Bishnoi, P. R. (1997). Kinetics
of carbon dioxide and methane hydrate formation. Canadian Journal of Chemical Engineering, 75, 1090}1096.
Masuda, Y., Fujinaga, Y., Naganawa, S., Fujita, K., & Hayashi, Y.
(1999). Modelling and experimental studies on dissociation of methane gas hydrates in Berea sandstone cores. Presented at the 3rd
International conference on gas hydrates. Salt Lake City, Utah. July
18}22.
Mehta, A. P., & Sloan, E. D. (1993). Structure H hydrate phase equilibria of methane#liquid hydrocarbon mixtures. Journal of Chemical
Engineering Data, 38, 580}585.
Mullin, J. (1997). Crystallization (3rd ed.). London: ButterworthHeinemann.
Ng, H. J., & Robinson, D. B. (1976). The measurement and prediction of
hydrate formation in liquid hydrocarbon}Water System. Industrial
and Engineering Chemistry Research, 15, 293}298.

4883

Nielsen, B., Svrcek, W., & Mehrotra, A. K. (1994). E!ect of temperature

and pressure on asphaltene particle size distributions in crude oils
diluted with n-pentane. Industrial and Engineering Chemistry Research, 33, 1324}1328.
Olsen, M. B., Majumdar, A., & Bishnoi, P. R. (1999). Experimental
studies on hydrate equilibria-carbon dioxide and its systems. International Journal for the Society of Materials Engineering and Resources, 7, 23}27.
Parrish, W. R., & Prausnitz, J. M. (1972). Dissociation pressures of gas
hydrates formed by gas mixtures. Industrial and Engineering Chemistry, Research, 11, 26}35.
Ripmeester, J. A., Ratcli!e, C. I., & Tse, J. S. (1998). The nuclear
magnetic resonance of 129Xe trapped in clathrates and some other
solids. Journal of the Chemical Society, Farraday Transactions, 84,
3731}3738.
Sloan, E. D. (1997). Clathrate hydrates of natural gases (2nd ed.). New
York: Marcel Dekker.
Trebble, M. A., & Bishnoi, P. R. (1987). Development of a new fourparameter equation of state. Fluid Phase Equilibria, 35, 1}18.
Trebble, M. A., & Bishnoi, P. R. (1988). Extension of the trebble}Bishnoi
equation of state to mixtures. Fluid Phase Equilibria, 40, 1}21.
Tse, C. W., & Bishnoi, P. R. (1993). Prediction of carbon dioxide gas
hydrate formation conditions in aqueous electrolyte solutions.
Canadian Journal of Chemical Engineering, 72, 119}124.
Ullerich, J. W., Selim, M. S., & Sloan, E. D. (1987). Theory and measurement of hydrate dissociation. A.I.Ch.E. Journal, 33, 747}752.
Van der Waals, J. M., & Platteeuw. J. C. (1959). Clathrate solutions.
Adv. Chem. Phys., 2, 1}21.
von Stackelberg, M., & MuK ller, H. R. (1954). Feste Gas Hydrate II.
Zeitschrift fuer Elektrochem, 58, 25}31.
Vysniauskus, A., & Bishnoi, P. R. (1983). A kinetic study of
methane hydrate formation. Chemical Engineering Science, 38,
1061}1072.
Vysniauskus, A. & Bishnoi, P. R. (1985). Kinetics of ethane hydrate
formation. Chem. Eng. Sci., 40, 299}310.