Chemical Engineering Science 59 (2004) 3849 3863

www.elsevier.com/locate/ces

Modelling hydrate formation kinetics of a hydrate

promoterwaternatural gas system in a semi-batch
spray reactor
Nimalan Gnanendran , Robert Amin
Woodside Research Facility, Department of Petroleum Engineering, Curtin University of Technology, GPO Box U1987, Perth WA 6845, Australia

Received 24 November 2003; received in revised form 23 January 2004; accepted 8 June 2004

Abstract
Hydrate formation kinetic modelling studies reported so far mainly concentrates on pure watergas systems in stirred-tank batch
environments. This work proposes a model for gas hydrate formation kinetics of a hydrate promoterwaternatural gas system in a semi-
batch reactor assuming steady-state, isothermal and isobaric conditions. The hydrate formation kinetics was modelled after extending
the recent method proposed by Kashchiev and Firoozabadi (J. Crystral Growth 241 (2002a) 220; J. Crystal Growth 243 (2002b) 476;
J. Crystal Growth 250 (2003) 499) for a single component gaswater system to a multi-component gaswateradditive system. The
extended Kashchiev and Firoozabadi model was applied for a semi-batch spray reactor here for the rst time. The hydrate formation
experiments were carried out in a pilot plant spray reactor at three different pressuretemperature regimes to determine the actual hydrate
formation kinetics in the spray reactor. The experiment results were then used to netune the adjustable parameters to facilitate accurate
model predictions.
2004 Elsevier Ltd. All rights reserved.

Keywords: Gas hydrates; Modelling; Formation kinetics; Spray reactor; Semi-batch; Hydrate promoter

1. Introduction conditions. This property of gas hydrates could be exploited

Gas hydrates are solid crystalline inclusion components
consisting of polyhedral water cavities which enclathrate
small gas molecules. Gas hydrates are formed at certain
pressuretemperature conditions where gas and water are
present. The petroleum industry has endeavoured the pre-
vention of hydrate formation in pipelines and processing
equipments. On the other hand, several researchers have
attempted to use hydrates as a means for gas storage
and transportation (Gudmundsson and Borrehaug, 1996;
Gudmundsson et al., 1998, 1999; Fitzgerald and Taylor,
2001). The amount of natural gas practically storable in
synthetic gas hydrates has a gas-to-hydrate volume ra-
tio of 165:1, measured at standard pressuretemperature
Corresponding author. Fax: +61-8-9266-4848.
E-mail address: nimalan@peteng.curtin.edu.au (N. Gnanendran).
0009-2509/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2004.06.009
for natural gas storage and natural gas transportation appli-
cations. The key focus of using hydrates as a storage or/and
transportation medium depends on the maximum possible
gas storable in hydrates and the rate of formation of these hy-
drates. The maximum amount of gas storable in hydrates is
limited by the theoretical gas-to-water ratio associated with
the three hydrate structures. Hydrates structure I, II and H
have an ideal gas to water molecular ratio of 8:46, 24:136
and 6:34, respectively (Sloan, 1998). Hydrates could be
formed with gas components partially lling the cages, and
also with un-reacted interstitial water remaining within the
hydrates.
The hydrate formation kinetics can be improved in a
watergas system by the addition of a hydrate promoter. The
hydrate promoting effect of hydrotrope para-toluenesulfonic
acid (pTSA) is discussed in one of our previous publi-
cation (Gnanendran and Amin, 2003). In another publica-
tion the thermodynamic modelling of the hydrate forma-
tion equilibrium conditions of the pTSAwatergashydrate
system is discussed (Gnanendran and Amin, 2004). This
3850 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863
work reports the hydrate formation kinetic modelling of the
pTSAwatergashydrate system in a semi-batch spray re-
actor as a nal chapter of the work on hydrate promoter
systems.
The hydrate formation kinetic modelling studies so far
have been developed based on stirred tank batch systems
(Englezos et al., 1987a,b; Skovborg and Rasmussen, 1994),
where a reactor containing water maintained at hydrate form-
ing conditions is injected with gas and agitated to produce
hydrates. This research utilises a pilot plant scale spray re-
actor (volume = 20 l) to produce powdery hydrates. The
reactor vessel is pressurised with natural gas and main-
tained at sub-zero temperatures where water mixed with the
hydrate-promoting chemical is sprayed, and gas hydrates
are formed during particle atomisation and deposition. The
spray process is selected to increase the water gas interac-
tion to yield higher hydrate formation rates. The experiments
were carried out with spraying pTSAwater solution in a
gas-pressurised reactor for a certain time period and subse-
quently allowing the reactor and its contents to stabilise for
a xed time period. The hydrates formed in the spray reactor
would not have to be subsequently separated from the wa-
ter using centrifuges or mechanical lters. The energy con-
sumption in a stirred-tank system with thick hydrate slur-
ries is a major drawback, whilst the spray reactor system is
much more attractive, especially for large-scale operations.
Further, with less moving mechanical parts, the capital and
running costs of the process is also minimal.
2. Model formulation
The hydrate formation modelling involves two main as-
pects: (i) modelling hydrate nucleation and growth kinetics;
and (ii) modelling the semi-batch spray reactor process. The
hydrate formation kinetics in a waternatural gas system in
the presence of an additive chemical is modelled rst, and
subsequently, the hydrate formation kinetics was incorpo-
rated into a steady state, semi-batch, isobaric, isothermal re-
actor model.
Hydrate nucleation is a microscopic process, during which
small hydrate crystals (nuclei) grow and disperse in an at-
tempt to achieve critical nuclei size for continued growth
(Sloan, 1998). The presence of non-polar molecules, such
as hydrocarbons, in water, distorts the water molecules in-
ducing them to arrange themselves into clusters (nuclei).
These clusters increase in number through a process of con-
tinuous fading and growing to a critical size before rapid
hydrate growth proceeds. The time taken for nucleation is
referred to as the induction time. The hydrate nucleation
process in practical situations is a heterogeneous nucleation
process, as homogeneity is rarely achieved. Therefore, in
the pTSAwaternatural gas system, its assumed heteroge-
neous nucleation takes place because of the presence of a
hydrate promoter in the system. Hydrate formation occurs
at the watergas interface, as the gas is present at its most
highest concentration in the interface, more so than in the
bulk liquid. The interface also lowers the Gibbs-free energy
which is conducive for hydrate nucleation.
Englezos and co-authors developed a mechanistic model
based on crystallisation kinetics and mass transfer effects to
predict the hydrate formation kinetics of methane and ethane
hydrates in a constant pressure stirred-tank gaswater system
(Englezos et al., 1987a,b). Later the model was simplied
by Skovborg and Rasmussen (1994) to a mass transfer lim-
ited model for multi-component gas mixtures. As part of this
research, the SkovborgRasmussen (1994) method, coupled
with the Michelsen stability criteria (Michelsen, 1982) for
the formation of a new phase, was used initially for the mod-
elling of hydrate formation kinetics in a natural gaswater
system. The scheme was developed in MathCad 2001i, and
when attempts were made to solve the Skovborg-Rasmussen
scheme, the ash calculations failed to converge, as the suc-
cessive substitution algorithm made the procedure unstable
in an oscillatory manner. According to Professor Michelsen,
this is due to the extremely strong negative deviations ex-
hibited by the hydrates from Raoults law (Michelsen, 2003).
Further, the SkovborgRasmussen (1994) scheme was de-
veloped for hydrate formation with pure watergas systems
in stirred-tank batch reactors, and the effects of additives
and process conditions of the semi-batch reactor could not
be incorporated into the model. Therefore, hydrate forma-
tion kinetics for the additivewaternatural gas system in a
semi-batch spray reactor was modelled using a more elabo-
rate scheme.
Kashchiev and Firoozabadi (2002a,b, 2003) recently pub-
lished a comprehensive study on hydrate nucleation and
growth kinetics based on classical nucleation and crystalli-
sation principles for single component gas hydrate systems.
The work also quantied the effects of additives in the
formation of hydrates when present in water, and distin-
guished how certain additives acted as hydrate promoters
while others acted as hydrate kinetic inhibitors (Kashchiev
and Firoozabadi, 2002b). The Kashchiev and Firoozabadi
model was developed based on a single gas component
system. The model was extended here for a natural gas
mixture.
The process system to be modelled is a semi-batch het-
erogeneous spray reactor for natural gas hydrate production
with continuous liquid ow into a pressurised vessel. The
semi-batch system or fed-batch system differs from a batch
system in the operation mode, as the reactants are charged
to the system at various times, and the products are removed
at various times in a semi-batch system. The hydrate forma-
tion experiments in the spray reactor were carried out as a
hybrid process, involving a spraying period and a stabilisa-
tion period. During the spraying period, the reactor operates
in a semi-batch mode, and during the subsequent stabilisa-
tion period, it operates in a batch mode. The rate limiting
reactant in the system is the pTSAwater solution, which
is injected into the system with time, whereas the natural
gas in the reactor is the second reactant present in excess in
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863 3851

the system for the hydrate formation reaction. When the Nozzle
spraying of the pTSAwater solution is stopped, the reactor
behaves as a batch system in the subsequent stabilisation pe-
riod. The hydrate formation and growth kinetics were mod-
elled in the spray reactor considering the above two modes
of operation. The modelling goal was to predict the overall
behaviour of the principle mass by determining the hydrate
formation volume factor (HFVF) or the gas-to-water ratio in

ht
hydrates, assuming the reactor behaved as an isobaric and
isothermal steady-state system.

2.1. Input material

Water is the main constituent of gas hydrates and it occu-

pies almost 80% by mass. p-Toluene sulfonic acid (pTSA),
Funnel
the hydrotrope used for hydrate promotion was mixed with

Hv
water to achieve a predetermined concentration (1.25 g/l).
The water pressure upstream of the nozzle was maintained
to achieve a predetermined spray pattern in the reactor, by
maintaining a constant pressure drop across the nozzle. The
nozzle area was heated to maintain the water temperature
just above the hydrate forming temperature to avoid block-
ages in the nozzle.
Natural gas (Nitrogen 2.60%, Carbon dioxide 2.19%,
Methane 84.23%, Ethane 6.79%, Propane 3.12%, n-Butane Test
0.41%, i-Butane 0.59%, i-Pentane 0.04%, n-Pentane 0.02%, Cylinder
n-Hexane 0.01%) was used to form hydrates to reect prac-
tical relevance as in our previous work (Gnanendran and
Amin, 2003, 2004). The reactor was pressurised to a prede-
termined pressure using natural gas, and allowed to cool to
a predetermined reactor temperature prior to the injection
of water.

Dv
2.2. Reactor

The reactor initially operated in a semi-batch mode, where

one reactant (natural gas) was charged to the reactor and
brought to predetermined test conditions. Subsequently, the
second reactant (water with additive) was injected continu-
ously to form the product (hydrates) in the reactor. A xed
stabilisation period of 5 min was maintained after the spray-
ing process for all the experiments, where the reactor be-
haved as a batch system. The product was then removed
from the reactor and transferred to a laboratory test cylinder
for HFVF measurements as described in Gnanendran and
Amin (2003).
2.2.1. Nozzle atomisation
Atomisation of the water was achieved using a nozzle unit
with a pressure atomisation or simplex type of nozzle. For
simplex nozzles, the following correlations for atomisation
parameters were obtained from Lefebvre (1989).
The Sauter mean diameter, SMD(m):
0.16 0.22
SMD = 4.4ST 0.6
0.16
L L QL
PL0.43 . (1)
Fig. 1. Schematic diagram of sample collection in the spray reactor.
The spray angle, c:

0.322
Ap
c = 60.076 . (2)
D s do
2.2.2. Particle ight and settlement
The particles formed due to atomisation were collected
in the cylinder-funnel arrangement placed in the reactor,
as shown in Fig. 1. The average distance travelled by the
particle was denoted by, ht, and the height and diameter of
the vessel were denoted as Hv and Dv , respectively.
The average ight time of the drops was calculated by
solving a system of two differential equations. The rst is
the resultant of the forces, acting on the drop, normalised
with respect to the volume of the particle. To simplify the
expression, the vertical falling path is considered and the
3852 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

nal model is not affected by this simplication. 2.2.3. Gaswater transport properties
(a) Diffusion coefcient of gas components in water: The
FT = F P F G F R . (3) diffusion coefcient of gas in water was calculated for the
The second equation is the rate of change in particle velocity, hydrate forming components using the WilkeChang corre-
which is expressed as lation, as given in Reid et al. (1987).

V = a.t v0 . 7.4 108 (MWw )1/2 T

(4) Dc = , (13)

w Vm0.6
Eqs. (4) and (5) can be expressed in differential form as the
following two equations, respectively: where  is the association factor of the solvent (for water
 = 2.6).

2
d2 x (w g) dx g An average diffusion coefcient for the gas into water was
=g 3Cd , (5) obtained by normalising the individual diffusion coefcient
dt 2 w dt 4wSMD
of the hydrate forming gas components, based on the gas
dx d2 x composition of the hydrate forming gas in the natural gas
= t 2 + v0 . (6)
dt dt mixture.
(b) Mass transfer coefcients of gas components in wa-
The distance travelled x(t) is calculated by solving the above
ter during spraying: The mass transfer coefcient of gas
system with the boundary conditions,
components in water droplets was calculated based on the
t = 0 at x = 0 and v = v0 . assumption that the droplets emerging from a spray noz-
zle were internally well mixed (Dimiccoli et al., 2000). The
The initial particle velocity exiting the nozzle is given by model proposed by Srinivasan and Aiken (1988) based on
(Lefebvre, 1989): Levichs theory (Levich, 1962), was used to determine the
 mass transfer coefcients of gas components in water. The
2
PN mass transfer coefcient is given as
v0 =  , (7)
P
0.16Dc 1/2
kL = Sc W e1/2 Re5/16 , (14)
where  is the nozzle geometry factor taken as 1.00. dp
The drag coefcient is calculated from the following cor-

w
relation as given in Perry et al. (1997): where Schmidt number: Sc = ,

 w Dc
24 vp2 w dp
Cd = , (1 + 0.14Re0.70
p ) Weber number: W e = ,
Rep 
for 0.1 < Rep < 1000, (8) dp vp w
Reynolds number: Re = .

w
where, Rep is the particle Reynolds number given by An average mass transfer coefcient for the gas was ob-
SMDv0  tained by normalising the individual mass transfer coef-
Rep = . (9) cients of the hydrate forming gas components, based on the

gas composition of the hydrate formation gas in the natural
The maximum ight time, tf , of a particle could be found gas mixture.
using the height (ht) travelled by the particle before reaching
the collection funnel. This could be found by solving: 2.3. Hydrate formation
x(t) ht = 0. (10) The hydrate formation operations to be modelled con-
The average ight velocity of such a particle during the sisted of two distinctive parts as mentioned above. The initial
ight could then be calculated from: phase was a semi-batch water injection (spraying) process,
and the second phase was a batch process, where the reac-
ht tor contents were maintained at reactor conditions, referred
aV = . (11)
tf to as the stabilisation period. A variable spray time and a
xed stabilisation time of ve minutes was used in the ex-
The lling rate in the reactor could also be calculated periments. When water mixed with the hydrate-promoting
assuming the sprayed particles were evenly deposited in the chemical was sprayed into the reactor and maintained at sub-
vessel bottom as zero temperatures, hydrate nucleation, as well as ice nucle-
Qw ation, occurred together. The overall quality of the hydrates
r= , (12)
bh (Dv/2)2 critically depended on the effective rates of hydrate and
ice nucleations, where faster hydrate nucleation rates and
where, bh is the hydrate bulk density. slower ice nucleation rates were intended for better quality
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863 3853

Therefore, the total number of gas components i per

Lw-H-V line water molecule is given as

Ni = 1 i,1 + 2 i,2 , (16)

Pexp, Texp
Pexp,Teq
where  is the number of cavities per water molecule (1 =
2/17 and 2 = 1/17 for structure II hydrates).
Pressure

Therefore, on a molar basis, the total moles of gas in

hydrates per mole of water could be calculated as
m

X = Ni . (17)
Peq,Texp i=1

The composition of the hydrate could also be calculated

Temperature as
 m 
Fig. 2. Identifying the driving force for hydrate formation in the g
For gas components : xi = Ni 1+ Ni
three-phase P .T diagram.
 m i=1
w
and for water : x = 1 1+ Ni (18)
i=1

hydrates. The formation of ice was inevitable in the spray 2.3.2. Supersaturation
reactor operation due to the low operating temperatures. The driving force for new phase formation is the differ-
Hydrate formation experiments were carried out at ence between the chemical potentials of the old and new
pressuretemperature conditions within the hydrate forma- phases. This difference is referred to as supersaturation
tion region, left of the thermodynamic equilibrium line, (

) and is dened for a single gas component system as
as shown in Fig. 2. For every hydrate forming system, (Kashchiev and Firoozabadi, 2002a):
the three-phase equilibrium line played a crucial part in


(Pr , T )Pr
determining the point where the actual hydrate formation

= kT ln +
e (Pr Pe ). (19)
occurred. The actual position of the point, indicated by
(Pe , T )Pe
x on the diagram, was determined by the heat and mass The supersaturation of the multi-component natural gas
transfer phenomena around the particle. Namely, the point system with m hydrate forming components was approxi-
approaches (Peq , Texp ) if the heat transfer resistance is neg- mated based on Englezos et al. (1987b) as
ligible (Englezos et al., 1987a). In the spray reactor, since



the hydrate formation experiments were conducted with

h
(P r , T )m P r
atomised water particles in a gas environment, the heat and

= kT xm ln +
e (Pr Pe ),
m

(Pr , T )m Pe
mass transfer resistance around the particles was safely as-
sumed to be minimal. Hence, it was assumed the hydrate (20)
particles were formed at (Peq , Texp ). where xmh is the water free mole fraction of gaseous compo-

2.3.1. Hydrate formation based on equilibrium
thermodynamics
The hydrate formation equilibrium for a pTSAwater
natural gas system can be predicted from a statistical ther-
modynamic model as described in Gnanendran and Amin
(2004), assuming structure II hydrates are formed in the
presence of natural gas components. Based on the proposed
thermodynamic model for the hydrate three-phase equilib-
rium, an equilibrium hydrate formation gas to water ratio
can be calculated at (Peq , Texp ) using the cavity fractional
lling calculation in the hydrate. The fractional lling of
cavities was found based on a Langmuir adsorption isotherm
(van der Waals and Platteeuw , 1959). The fractional lling
of component i in cavity type c (c = 1, 2) is given as
eq
Ci,c f
i,c = m i eq .
1 + i=1 Ci,c fi
nents in hydrate.

e is calculated for a gas mixture as

e = nw vw vh , (21a)
where nw is the is the hydration number of structure II hy-
drates, vw the volume of water molecule, and vh is the vol-
ume of a hydrate building unit given as
vcell
vh = , (21b)
ng
where vcell is the volume of hydrate unit cell, ng the stoi-
chiometric number of gas molecules at equilibrium condi-
tions Pe , T taken as ng = 136.
The supersaturation

of the system is assumed to be a
time-independent parameter regardless of the mode of op-
eration in the reactor, and it depends mainly on the reac-
(15) tor pressure and temperature (which are assumed constant)
along with the hydrate structural properties as seen above.
3854 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

hg 2.3.4. Hydrate formation in the semi-batch environment

The volume of water in the system at any time during the
Gas
0 sg operation is given as

Solution n Qt for t
ti ,
V (t) = (28)
V (ti ) for t > ti .

(a) Gas concentration: The mole fraction of gas dissolved

in water (xiw ) at equilibrium conditions could be calculated
Fig. 3. Schematic diagram of n building units in heterogeneous nucleation from Henrys Law equations. The concentration of gas com-
at the solution/gas interface. ponents (m3 ) at equilibrium conditions could be then cal-
2.3.3. Nucleus and clusters culated as
The hydrate formation in the system of sprayed water


eq w
particles in a gas eld would undergo a heterogeneous nu- Cg,1 = Cw 0
xi AvN (29)
cleation process occurring at the gassolution interface. The i
lens-shaped hydrate nucleation clusters of n units is shown
(b) Kinetic parameter for heterogeneous nucleation:
in Fig. 3, along with the wetting angles ( and 0 ) with re-
The kinetic parameter of equal size heterogeneous nucle-
spect to each phase, where  is the specic surface energy
ation particles is given by the correlation in Kashchiev and
of the hydratesolution interface, sg is the specic surface
Firoozabadi (2003). The kinetic parameter is given as
energy of the solutiongas interface, and hg is the specic
surface energy of the hydrategas interface. 1/3 eq Ap C p
For lens-shaped clusters the wetting angles are given in A1 = Z (4c)1/2 vh DcC g,1 ns 1/3 , (30)
aw
Kashchiev and Firoozabadi (2002b) as
where Z is the Zeldovich factor calculated from Kashchiev
(2sg + 2 2hg ) and Firoozabadi (2002a):
cos  = , (22)
2sg 
1/2
W
(2sg 2 + 2hg ) Z= , (31)
3kT ns2
cos 0 = . (23)
2sg hg
Cp is the concentration of nucleation active particles ( m3 )
The effective specic surface energy of the system is is given by the concentration of the surface-active pTSA
given by concentration as
ef =  (24) Cp = CTSA AvN, (32)
where  is the wetting factor (0 <  < 1) and for lens-
where CTSA is the concentration of pTSA in moles/m3 , aw
shape clusters it is given by
is the area occupied by a water molecule on the solution/gas

interface, which is given as
= (1/4)(2 + cos )(1 cos )2 + (1/4)(2 + cos 0 )

1/3
9vw2

3 1/3 aw = (33)
sin  16
(1 cos 0 ) 2
. (25)
sin 0 (c) Nucleation rate: The nucleation process is classied
The nucleus size for hydrate nucleation could be deter- as progressive nucleation as opposed to instantaneous nucle-
mined from the nucleation theory given in Kashchiev (2000) ation according to Kashchiev and Firoozabadi (2003), and
as the rate of nucleation (m3 s1 ) is given as



8c3 vh2 3ef

4c3 vh2 3ef

ns = , (26) J1 = A1 exp exp . (34)
27

3 kT 27kT

2
where c = (36)1/3 assuming spherical nuclei, h is the (d) Crystal growth rate: The time dependence of the crys-
volume of hydrate building unit. tallite nucleation rate, based on the power law for crystallite
Nucleation work, W , is the energy barrier needed to growth is given as
achieve the above nucleus size for nucleation, which is
given as (Kashchiev and Firoozabadi, 2002a) g(t) = mGm t m1 , (35)
4c3 vh2 3ef where, m is a number where m > 0 and G is the growth
W= . (27)
27

2 constant.
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863
The above constants m and G can be obtained by con-
sidering the existing kinetics of crystallite growth. For lin-
early increasing crystallite radius with time, m=1 and G is
the time-independent growth rate of the separate crystallites.
As discussed above, the hydrate formation process con-
sists of a spraying period and a post-spraying stabilisation
period. The nucleation kinetics of these two situations is
distinct, therefore they are analysed separately.
(e) Crystal growth constant during spraying: The growth
constant, G1 , for the sprayed particles in a gas environ-
ment was assumed to be similar to the volume diffusion of
dissolved gas through a stagnant layer formed when the so-
lution was agitated. A correlation for such a growth con-
stant, G1 , is given in Mullin (1993) and recommended by
Kashchiev and Firoozabadi (2003) is used here. The growth
rate correlation is given as


eq


3855
By substituting Eq. (28) in (41), the semi-batch system could
be reduced into a differential form as follows:
dCw (t)
t + (1 + ke1 (t)t)Cw (t) = Cw0 . (42)
dt
The differential equation could be iteratively solved with
the boundary condition Cw (0) = Cw0 for the varying rate
constant given in Eq. (40) to determine the concentration of
water, Cw (t), at any given time during water injection. The
concentration of gas, which forms hydrates, could be then
found per reaction volume from:
Cg (t) = (Cw0 Cw (t)) . (43)
2.3.5. Hydrate formation in the batch environment
During the post-spray period, where product stabilisation
occurs, the system is similar to a batch hydrate nucleation
system. The time-independent concentration of dissolved
G1 = (vh ak l Cg,1 ) exp 1 and m 1. (36) gas in the remaining un-crystallised water could be calcu-
kT lated from

(f) Fraction of solution crystallised: The fraction of the 

eq w
initial amount of substrate crystallised at a given time in a Cg,2 = Cw (ti ) xi AvN (44)
xed volume is given as (Kashchiev and Firoozabadi, 2003) i

  and the kinetic parameter would be

bG3m J
(t) = t 1+3m , (37) Ap Cp
(1 + 3m) 1/3 eq
A2 = Z (4c)1/2 vh DcC g,2 ns1/3 (45)
aw
where, b is the shape factor of crystals and given as
and subsequently the nucleation rate could be found from
4


b= . (38)

4c3 vh2 3ef

3 J2 = A2 exp exp (46)
kT 27kT

2
Therefore the hypothetical, time-dependent, crystallised vol-
ume fraction, during any given time t (
ti ), in the spraying The growth constant, G2 , is given by the correlation pro-
period could be found after considering the differential vol- posed by Kashchiev and Firoozabadi (2003) for undisturbed
ume crystallised at time t (0 < t < t) and integrating within volume diffusion of dissolved gas toward spherical crystals.
the time interval 0 < t < t (Kashchiev, 2000): The relationship is given as


bG3m


1 J1
eq
1 (t) = t 1+3m . (39) G2 = (2vh aDcCg,2 ) exp 1 and n = 0.5 (47)
(1 + 3m)(2 + 3m) kT
and the volume fraction crystallised during the stabilisation
(g) Hydrate formation rate constant: The hydrate
period is given as
formation rate constant at any given time during the  
spraying period could be then found by differentiating the
2 J2
bG3n
fraction crystallised with respect to time: 2 (t) = t 1+3n . (48)
(1 + 3n)
d 1 (t)
ke1 (t) = . (40) The rate constant at any given time during the stabilisation
dt period of the hydrate formation process could be calculated
(h) Semi-batch reactor modelling: The variable reaction as
volume during the spraying period is given by Eq. (28) for d 2 (t)
t
ti as ke2 (t) = (49)
dt
V (t) = Qt 2.3.6. Overall hydrate formation
The initial amount of gas in the reactor could be calculated
Mole balance of water in the semi-batch system at any given at the reactor pressuretemperature conditions using the real
time, t, could be written as (Froment and Bischoff, 1990) gas law equation:
d(V (t)Cw (t)) Pr V r
= QC 0w V (t)ke1 (t)Cw (t). (41) Mg0 = , (50)
dt zRcT
3856 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

where V r is the reactor volume calculated based on the Table 1

reactor dimensions. Reactor dimensions
The moles of water crystallised, Mwc (t), during the whole Reactor vessel height, Hv 880 mm
process could be calculated as Reactor vessel diameter, Dv 173 mm
Distance travelled by spray, ht 350 mm
Mwc (t)

(Cw0 Cw (t))Qt for t
ti ,
= c (51)
Mw (ti )[1 + (ke2 (t ti ))(t ti )] for t > ti . Table 2
Simplex nozzle dimensions
The moles of gas in hydrates at any given time t, Mgh (t), Total inlet port area, AP 2.5 mm2
could be then calculated as Inlet chamber diameter, Ds 4.0 mm
Exit orice diameter, do 0.3 mm
Mgh (t) = Mwc (t) , (52)

where, is the equilibrium gas: water mole ratio in hydrates

at (T , Peq ) as determined in Eq. (17).
Moles of water remaining in the system, which would be
in the form of ice, could be calculated at any given time as
follows:
Mwr (t) = Mwi (t) Mwc (t).
Similarly, the moles of gas remaining in the vessel could be
calculated as follows:
Mgr (t) = Mg0 (t) Mgh (t).
The amount of hydrates formed could be also calculated
from the equilibrium gas water mole ratio, . The hydrate
reaction equation could be written as
Gas + (1/ )Water Hydrates.
Therefore, the moles of hydrates formed could be then
calculated as
M c (t)
Mh (t) = w .
1/ where, Pg is the reactor pressure in psig.
The hydrate formation volume factor, HFVF(t), or the gas
to total water volume ratio at standard conditions, could be
then calculated assuming the ideal gas law as
Mgh (t)(Rc(Ts )/Ps )
HFVF(t) =
Qt i
2.4. Evaluation of model parameters
The model parameters are the geometrical dimensions and
physical constants used in developing the model. These pa-
rameters were obtained from physical measurements or from
literature, details of which are given in this section.
2.4.1. Reactor vessel dimensions
The reactor vessel schematic drawing, with important di-
mensions, is given in the previous chapter. The dimensions
used in the model is given in Table 1.
2.4.2. Spray characteristics
The nozzle dimensions play a crucial part in determining
spray characteristics. The nozzle used in the reactor experi-
ments was a simple garden reticulation nozzle bought from a
local hardware store. Therefore, the nozzle dimensions were
(53) obtained from their physical measurements and are shown
in Table 2 .
The spray angle was calculated using the above dimension
using Eq. (3) and compared with the physical spray angle
measurements and were found to be approximately equal.
(54) The properties of the solution were assumed to be similar
to the properties of water due to the very small amount of
pTSA present in the solution.
The SoaveRedlichKwong (SRK) equation of state
was used to determine the gas phase properties. Refer to
Gnanendran and Amin (2004), for SRK equation of state
and SRK model parameters used in this work. The dynamic
viscosity of gas near zero-temperatures was correlated for
various pressures using the following correlation:

g = 2 1013 Pg2 + 9 1011 Pg + 1 106 Ns/m2
(55)
The average bulk density of hydrates deposited in the
vessel was measured in the pilot plant as 0.6 g/cm3 .
2.4.3. Hydrate formation
The molar volume of gas components at their boiling
(56) points was calculated after determining the density of the
gas component at its boiling point. The density correlation
for organic liquids at a given temperature was obtained from
Perry et al. (1997).
The thermodynamic model used for predicting the hy-
drate equilibrium pressure at a given temperature for a
pTSAwaternatural gashydrate is given in Gnanendran
and Amin (2003b), along with the model parameters used
for calculating the thermodynamic equilibrium.
When calculating the supersaturation, the volume differ-
ence between water molecules in the solution and the hy-
drate building unit in the hydrate crystal at Pe and T ,
e , in
Eq. (17) was calculated using hydrate structure II properties
(Sloan, 1998).
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863 3857

Table 3 3. Experimental
Hydrate nucleation parameters

Parameter Value The hydrate formation experiments were carried out in the
hydrate pilot plant spray reactor developed at Curtin Univer-
Hydration number, nw 136/24
sity of Technology. Details of the hydrate pilot plant and the
Volume of water molecule, vw 0.03 nm3
Volume of hydrate unit cell, vcell 5.18 nm3
experiments in the spray reactor are given in Gnanendran
Surface energy of solution/gas, sg 70 mJ/m2 (2003). A brief description of the experiment set-up and the
Surface energy of hydrate/gas, hg 80 mJ/m2 results are given in Fig. 4.
Surface energy of solution/hydrate,  15 mJ/m2
Sticking coefcient,  1.0
Area of a nucleation active particle, Ap 0.1 m2
3.1. Experiment procedure

The test cylinder/funnel arrangement (as shown in

The surface energies of the interfaces in the pTSAwater
Fig. 1) was loaded into the cleaned reactor vessel and the
gashydrate system are the key parameters which affect hy-
vessel bottom door was secured. The vessel was purged
drate nucleation and crystal growth rates. There were no
using compressed natural gas via V3, while all the other
direct measurements possible for these parameters in this
valves were kept closed and valve V7 was kept open. After
research, and these parameters were assumed based on pre-
purging, valve V7 was closed and the vessel was pressurised
vious publications. The presence of a surface-active agent
to a pressure slightly above the experiment pressure, then
was found to lower the surface energies of the system, thus
valve V3 was closed and the vessel was allowed to cool to
lowering the effective surface energy. The surface energy of
the experiment temperature. The additivewater solution of
solution-gas, sg , was taken as 70 mJ/m2 as suggested by
concentration 1.25 g/l pTSA in water was then dynamically
Kashchiev and Firoozabadi (2002b) for water/methane sys-
saturated in the two saturation vessels with natural gas. To
tems. For cap-shaped clusters favouring heterogeneous nu-
archive this, a predetermined amount of pTSAwater solu-
cleation, the surface energy of hydrate/gas, hg , was taken
tion was rstly drawn to the two saturation vessels using
as 80 mJ/m2 a reduced value from the suggested surface
the vacuum pump, where valves V2 and V6 were kept open,
energy 90 mJ/m2 in the above publication. The above au-
and the rest of the valves were kept closed. Then the water
thors also used a value of 20 mJ/m2 for the surface energy
saturation vessels were pressurised to a predetermined pres-
of solution/hydrate, , based on the ice/water nucleation sys-
sure of 50 psi (344.74 kPa) above the reactor pressure, using
tem (Mason, 1971). In this work, to incorporate the hydrate
valve V1, while the rest of the valves were kept closed.
promoting effect of the pTSA hydrotrope, it was assumed
Then the water was circulated for a period of 30 min, using
that the additive adsorbs onto the nucleus surface and de-
the pump and opening valves V2 and V8 while keeping the
creases the solution/hydrate surface energy, , and a value
rest of the valves closed. After the saturation period, gas
of 15 mJ/m2 was used in the model.
pressure was used to inject the water into the reactor vessel
The above surface energy value reduces the effective sur-
by opening valves V1 and V5, while keeping the rest of
face energy, ef , which in turn increases the nucleation rate,
the valves closed. The needle valve V4 was used to achieve
J , in Eqs. (34) and (46), thus promoting the formation of
accurate control of the up-stream nozzle pressure, thus
hydrates in the system.
maintaining a constant pressure drop of 30 psi (206.84 kPa)
The following values were used in determining the kinetic
across the nozzle. The spraying time, vessel pressure and
parameter, A, in Eqs. (30) and (45). The value suggested
vessel temperature were the key variables recorded during
for the sticking coefcient, , in Kashchiev and Firoozabadi
the tests. After injecting the saturated water, the vessel was
(2002b) of 1.0 was used. The area of a nucleation active par-
allowed to rest for a period of 5 min for post-injection satu-
ticle, Ap , which is the area of pTSA particle, was taken to be
ration and then the gas was vented. The hydrates were then
0.1 m2 , based on the assumption that the ratio pTSA:water
transferred from the reactor vessel to the laboratory cylin-
molecular area is proportional to their molecular weights
der and HFVF (gas-to-water volume ratio) measurements
which is approximately a 10:1 ratio. The water molecule
were recorded for each operation (refer to Gnanendran and
has an area of approximately 0.01 m2 (Kashchiev and
Amin, 2003 for HFVF measuring procedure).
Firoozabadi, 2002b).
The model parameters related to hydrate formation kinet-
ics are summarised in Table 3 .
The crystal growth parameter, m and n, for growth 3.2. Experiment results
constant G1 in semi-batch phase (Eq. (36)) and G2 in the
stabilisation period (Eq. (47)), were assigned as adjustable The experiments carried out at three-different pressures
parameters. The values of these parameters were obtained along with the experiment conditions are averaged from
based on the concrete kinetics of the hydrate formation pro- three tests for each case. The results along with the average
cess. absolute deviations (AAD) are summarised in Table 4.
3858 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

Fig. 4. Schematic diagram of the Curtin hydrate pilot plant.

Table 4
Hydrate pilot plant experiment summary

Injection time Injection rate Temperature Pressure HFVF

(min) (m1/min) ( C) (psig) (y/v)

Case Value AAD Value AAD Value AAD Value AAD Value AAD
I 20.0 0.0 25.0 0.0 15.2 0.9 408 3 91.76 4.40
II 14.0 1.3 60.7 14.2 0.2 0.5 828 2 137.98 3.00
III 13.3 2.2 72.1 28.6 0.8 1.0 1248 16 156.73 16.40

4. Model evaluation
The pilot plant experimental results and the model pre-
dictions are compared in this section to evaluate the perfor-
mance of the model. The input parameters were taken from
the pilot plant operating experiments, and the adjustable
parametersthe rate components m and n were adjusted
up to three decimal points to obtain the HFVF results. For
calculations of the equilibrium pressure at the given tem-
perature of the 1.25 g/l pTSAwaternatural gas system,
the micelle size (micelle aggregation number)a thermo-
dynamic model parameter, was determined as 740 accord-
ing to Gnanendran and Amin (2004). The important model
parameters are summarised in Table 6.
The growth components m and n were adjusted such
that 0 <
(t) < 1 in the semi-batch and batch periods, re-
spectively to obtain the HFVF values within the average de-
viations of the pilot plant experiment results. The adjustable
parameters have deviated positively from the ideal crystal
growth systems but remain closer to the ideal crystal growth
systems (m 1 and n 0.5).
The adjustable parameters, the growth rate components
m and n, showed strong linear dependence on reactor
temperature as seen in Fig. 5. This conrms the strong im-
pact of the system temperature in the hydrate formation pro-
cess compared to pressures.
The following common parameters for all three cases are
shown in Table 6.
The spray cone angle was equal to the approximate physi-
cal measurements at ambient conditions. The higher value of
the hydrate/solution wetting angle, , and lower value of hy-
drate/gas wetting angle, 0 , suggests the cap shaped hydrate
nuclei is predominately dissolved in pTSA/water solution.
The lower value of effective surface energy, ef , favours hy-
drate nucleation, thus promoting hydrate formation.
4.1. Reactor simulation curves
The following curves were obtained from the MathCad
2001i worksheet, for the reactor contents and hydrate for-
mation volume factors (HFVFs) for each of the above three
cases: (refer Table 5output parameters for notations) (see
Figs. 611 ).
An important observation gleaned from the above curves
is the initial induction time period for hydrate nucleation.
During this period, negligible hydrate formation occurs and
subsequently the exponential hydrate crystal growth follows,
as shown in Figs. 7, 9, and 11. The induction time for hydrate
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863 3859

Table 5
Hydrate reactor model parameters and predictions

Model parameters Case I Case II Case III

Description Notation Units

Input parameters
pTSA concentration g/l 1.25 1.25 1.25
Pressure Pi psig 408 828 1248
kPa 2913 5809 8705
Temperature T C 15.2 0.2 0.8
Water ow rate Q ml/min 25.0 60.7 72.1
Injection time min 20.0 14.0 13.3
ti sec 1200 840 798
Pressure drop across nozzle
P i kPa 207 207 207
Micelle aggregation size ms 740 740 740

Adjustable parameters
Semi-batch rate component m 2.107 1.635 1.574
Batch rate component n 0.862 0.752 0.751

Output parameters
Initial moles of gas in the Mgi mol 31.786 65.038 106.889
reactor
Total moles of water injected Mwi mol 27.778 47.211 53.274
Mole of water crystallised in Mwc mol 15.424 39.400 49.793
time (ti+ts) (ti+ts)
Moles of gas in hydrates in Mgh mol 1.884 4.711 6.051
time (ti+ts) (ti+ts)
Mole of gas remaining in the Mgr mol 29.902 60.327 100.839
reactor at time (ti+ts) (ti+ts)
Moles of water remaining Mwr mol 12.354 7.811 3.481
Moles of hydrates formed at Mh mol 1.884 4.711 6.051
time (ti+ts) (ti+ts)
Water crystallised to hydrates  % 56.5 83.4 93.5
Hydrate formation volume HFVF 93.36 137.35 156.33
factor at time, (ti+ts) (ti+ts)

2.2 Table 6
Model predictions constant parameters
2
y = -0.0325x + 1.6138 Description Notation Units Values
1.8
R2 = 0.9976
Component value

1.6 Half cone angle of spray c degree 47.4

Semi-Batch component, m Hydrate/solution wetting angle  degree 127.4
1.4
Batch component, n Hydrate/gas wetting angle 0 degree 8.6
1.2 Linear (Semi-Batch component, m)
Wetting Factor  0.967
y = -0.0071x + 0.7537 Linear (Batch component, n) Effective surface energy ef mJ/m2 14.01
1
R2 = 0.9977
0.8

0.6

0.4
-16 -14 -12 -10 -8 -6 -4 -2 0 2 nential growth rate in the above simulations. However, if
Temperature dynamic modelling of the reactor is attempted with non-
isothermal conditions, an exponential decay of hydrate for-
Fig. 5. The temperature dependence of adjustable parameters.
mation with time could be anticipated.

nucleation can be found from the above curves initial at 4.2. Model predictions
portion as shown in Table 7.
The hydrate formation in the semi-batch and batch phases The model was also used to study the inuences of input
for the isothermal and isobaric conditions shows an expo- parameters on the hydrate formation. The following patterns
3860 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

35 150

30
Mwi(s)
Mwc(s)
25 100
Mgh(s)
Mgr(s) HFVF(s)
20

50
15

10

0
5 0 200 400 600 800 1000 1200 1400
s ti+ts

0
Fig. 7. Hydrate formation in the reactor with time, for Case I.
0 200 400 600 800 1000 1200 1400
s ti+ts

Fig. 6. Reactor components variation with time, for Case I.

70
60
Mwi(s)
were observed from the model:
Mwc(s)
Mgh(s)
The increase of reactor pressure, or the decrease of reac- 40
Mgr(s)
tor temperature, increases the supersaturation (Eq. (20)),
which in turn reduces the nucleation work (Eq. (27)) and
increases the nucleation rate (Eqs. (34) and (46)), there- 20
fore increasing the rate of hydrate formation.
The increase in the distance travelled by the particle during
spraying increases the average ight velocity, which in turn 0
0 100 200 300 400 500 600 700 800 900 1000 1100
increases the mass transfer coefcient (Eq. (14)), and the s ti+ts
improved mass transfer rate increases the hydrate growth
rate (Eq. (36)) during the spraying period. Fig. 8. Reactor components variation with time, for Case II.
The increase in pressure drop across the nozzle reduces
the mean diameter of the spray particles, which in turn
increases the mass transfer coefcient (Eq. (14)), and the
improved mass transfer rate increases the hydrate growth 150

rate (Eq. (36)) during the spraying period.

The increase in the water injection rate shows an increase
in the rate of hydrate formation in the above isothermal
100
model. However, note that this would not be the case in
the real system, as the heat removal in a real system would HFVF(s)
not be perfect, thus causing the temperature of the reac-
tor contents to increase, which in turn would reduce the 50
hydrated formation rate.
The increase in the post spraying stabilisation period in-
creases the overall hydrate formation, but the exact rate
0
of increase depends on the concrete kinetics component 0 100 200 300 400 500 600 700 800 900 1000 1100
(given as exponent n in the above model), observed in s ti+ts
the real system.
Fig. 9. Hydrate formation in the reactor with time, for Case II.
The reduction of surface energy values, due to the pres-
ence of the pTSA surface-active agent in the system, has
shown that hydrate formation rates could be improved. The
rate of hydrate formation is highly sensitive to the effective sensitive to the system temperature and, as seen in Fig. 5,
surface energy, ef , and a reduction in this parameter would the values of the rate components m and n are dictated
improve the hydrate formation rate. The model is also hyper by the reactor temperature rather than the reactor pressure.
 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863 3861

110 librium hydrate gas to water ratio. The pilot plant exper-
100
Mwi(s) iment results were used to determine the concrete growth
Mwc(s) kinetics exhibited in the real system and were incorporated
Mgh(s) into the model in the form of adjustable parameters. There-
Mgr(s) fore the model proposed here could be adapted with any gas
hydrate formation system after experimentally determining
50
the actual kinetic parameters. The experimental determina-
tion and application of accurate surface energy values of the
additivewatergas system would also render better practi-
cal results from the model. The spray reactor hydrate form-
0
ing process coupled with a adequate kinetic model for the
0 100 200 300 400 500 600 700 800 900 1000 hydrate promoterwatergas system could be used for var-
s ti+ts ious synthetic gas hydrate production technologies, such as
for CO2 sequestration, gas separation, along with natural gas
Fig. 10. Reactor components variation with time, for Case III. hydrates storage and transportation.

200
Notation

150 a acceleration
A kinetic parameter for hydrate nucleation
Ap total inlet port area
100 HFVF(s)
ak L average mass transfer co-efcient
aDc average diffusion co-efcient
AvN Avogadros number
50
b shape factor of crystals
c constant for spherical nucleus
0
C Langmuir constant, concentration
0 100 200 300 400 500 600 700 800 900 1000 Cd drag-coefcient of the medium
s ti+ts Dc diffusion coefcient
Ds inlet chamber diameter of nozzle
Fig. 11. Hydrate formation in the reactor with time, for Case III.
Dv internal diameter of the vessel
d diameter
Table 7 f fugacity
Induction time for hydrate nucleation FT resultant force
Case I Case II Case III FP weight of the particle
FG buoyancy force
Induction time(s) 610 380 370 FR resistance force of the medium
g acceleration due to gravity, crystal growth rate
G crystal growth constant
5. Concluding remarks ht sample collection height (particle ight distance)
H Henrys law constant
The hydrate formation kinetics was modelled using the Hv height of the vessel
recent work of Kashchiev and Firoozabadi (2002a,b, 2003), HFVF hydrate formation volume factor (gas to water vol-
incorporating the effects of additives in hydrate formation ume ratio)
when present in the liquid phase. The Kashchiev and Firooz- J rate of nucleation
abadi model deals with one-component-gas/water systems k Boltzmanns constant, J/K
in batch environments, and it was extended here and used for ke rate constant
a multi-component natural gas mixture in a semi-batch sys- kL mass transfer co-efcient
tem. The hydrate formation kinetics was then coupled with m micelle aggregation size, growth rate exponent for
an isobaric, isothermal semi-batch spray reactor system in injection period
this work to successfully predict the behaviour of the pilot MW molecular weight
plant experiment results. The model determines the amount M moles of a component
of water crystallised (product formed) using the hydrate for- n number, growth rate exponent for stabilisation pe-
mation kinetics in the semi-batch system, and subsequently riod
the amount of gas in the hydrates was found from the equi- N total number of gas components per water molecule
3862 N. Gnanendran, R. Amin / Chemical Engineering Science 59 (2004) 3849 3863

ns nucleus size n cavity type (n = 1 or 2), growth constant during

P pressure stabilisation period
pTSA para-Toluene sulfonic acid N nozzle
Q water ow rate, m3 /s o property at reference condition, initial condition,
r rate of lling orice
Rc universal gas constant p particle
Re Reynolds number r reactor, remaining
Sc Schmidt number s standard conditions
ST surface tension, kg/s2 sg solutiongas interface
SMD Sauter mean diameter TSA toluene sulfonic acid
SNGH synthetic natural gas hydrates w, W water
t time 1 nucleation properties during the spraying period
ti injection time 2 nucleation properties during the stabilisation period
ts stabilisation time
T temperature, K
v velocity, m/s, volume Acknowledgements
V volume of water
Vm molar volume at normal boiling point, cm3 /mol The authors wish to thank Woodside Petroleum Ltd., the
W nucleation work project sponsor, for their continuing support to the Gas Hy-
We Weber number drate Project at Curtin University of Technology, Western
x liquid phase mole fraction, vertical distance trav- Australia and their cooperation in publishing this paper.
elled, water free hydrate mole fraction
y gas phase mole fraction
z z-factor References
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