Advances in Ma terials Physics and Che mist ry, 2012, 2, 244-247
doi:10.4236/ampc.2012.24B062 Published Online December 2012 (htt p://
Copyright © 2012 SciRes. AMPC
Developing a Mathematical Model for Hydrate Formation in
a Spray Batch Reactor
Mohammad Ka zemeini1, Far ideh Freidoonian2, M oslem Fattahi1
1Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran
2Islamic Azad University, South Tehran Branch, Tehran, Iran
Received 2012
The formation of methane hydrate was undertaken in this research. The purpose of this work was to model the methane hydrate for-
mation with a hydrate-watermethane system in a semi-batch reactor under steadystate, isothermal and isobaric conditions. Ob-
tained results were validated wit h experiments con ducted in a semi-batch spray reactor at low temperatures and high pressures. The
investigated formation of gas hydrate from pure methane required physical constants of these materials which were determined
throu gh experimen tal d ata. The e xperiment s hence, the th eoret ical calcul ation s were con du cted with pu re methane an d carried out in
a spray reactor at 273.95K and 8705kPa to determine the actual amount of hydrate formation in such reactor. Ultimately; the com-
parison of the results generated from the developed mathematical model with those of experimental data of others indicated a very
satisfactory agreement obtain ed.
Keywords: Hydrate Formation ; Methane; Spray Reacto r ; Semi-batch; Modeling
1. Introduction
Hydrate are crystalline water-based solids physically resem-
bling ice, in which low molecular weight (light) gas molecules
are trapped by water molecules bounded by hydrogen and sta-
bilized due to Van-der-waals forces. In hydrate formation host
molecule is water and guest molecule i s a gas or liqu id [1].
Thermodynamic conditions of hydrate formation are often
found in pipelines. It is unfavorable because these crystals
might plug the flow line and damage valves and instrumenta-
tion. Hydrate formation within pipelines slows down the flow
of materials due to blockage causing significant economic
losses. Hydrate might be used for gas storage and transportation
as well. Utilizing hydrate as a storage mean for transportation
depends upon the maximum gas storable through hydrate and
the hydrate formation rate. Research in this area started at be-
ginning of the 1990s. Gudmundsson and his group at Norwe-
gian University reported results of experimental investigations
on production, storage and transportation of gas hydrates [2,3].
The hydrates are to crystallize in 3 structures, I, II and H,
depending upon the nature and the size of guest molecules [4,
5]. A unit cell of structure I contained eight cavities (two smalls
and six large ones) and formed by 46 hydrogen-bonded water
molecules. While a uni t cell of structure I I contained 136 water
molecules and enclosed 24 cavities including 16 smalls and 8
large ones. The gas molecules of methane, ethane, propane,
isobutene, CO2, H2S, and N2 were known to stabilize t he micro
cavities formed b y either of th e two hydrate structu res.
The formation of either of structures I or II is related to the
ratio o f th e guest molecule to t he cavity size whi le the ther mo-
dynamic operating conditions including temperature, pressure
and gas composition are also very important affecting forma-
tion of these structures.
The kinetic models of hydrate formation studied previously
have been developed based upon stirred tank batch systems [6].
Such reactors included water at hydrate formation conditions
being injected along with the gas for production of the hydrates.
Natural gas hydrate formation condition was usually deter-
mined experimentally in the laboratory however; such data
were not always available. Hence, correlations utilized in ord er
to determine values for the natural gas hydrate formation condi-
Hydrate formation kinetics usually improved through addi-
tion of a promoter. One of the most popular promoters was
paratoluenesulfonic acid (pTSA) which was undertaken in the
presen t research. The work repo rted her e therefore; d escribed a
theoretical analysis for the methane hydrate formation in pres-
ence of the pTSA, the results for which were compared with
experimental data available in the open literature to verify the
2. Theore tical Ba ckgrou n d
The mathematical model of the hydrate formation in this work
included two main steps of: (1) nucleation and growth model-
ing of hydrate and (2) modeling of a semi-batch spray reactor
process. The presence of non-polar molecules such as hydro-
carbons in water distorted water molecules to organize them-
selves into clusters forming the needed nuclei. The nucleation
time named induction period. Furthermore, due to the highest
concen tration of gas at th e water-gas interface, th e hydrate for-
mation took place at this location. The process to be modeled
was then a semi-bat ch hetero geneous spray reactor for methane
hydrate production into a pressurized vessel. This process in-
volved a spraying period during which the reactor operated in a
semi-batch mode and a stabilization period during which the
Co pyr i g ht © 2012 SciRes. AMPC
reactor operat ed in a bat ch mode.
2.1. Materials
The main component of methane hydrate was water which
occupied around 80% by mass and the remainder devoted to
methane. The simulated promoter mixed with water was the
pTSA with predetermined concentration of 1.25g/l. Pure meth-
ane was also uti lized to form hydrates.
2.2. Apparatus
Figure 1 showed a schematic drawing of the experimental ap-
paratus leading to the present investigation. A known amount
of water was fed into the reactor, which was purged continu-
ously with the pure methane. The reactor operated in a semi-
batch mode. A fixed stabilization period of 5min was main-
tained after spraying, where the reactor behaved as a batch
system to form the product [7].
3. Computational Proced u res
In this simulation the MATLAB software of version 2011 to
calculate the correlatio ns of hydrate formation was utilized. As
mentioned above, initial phase of hydrate formation was
semi-batch water injection or spraying process, and the second
phase was a batch process requiring stabilization period. The
injection time, ti, for spraying period was determined to be 798s
and the induction time, ts, for stabilization period was found to
be 370s. Water molecules with initial velocity were accounted
for to travel the horizontal distance thru the reactor. During this
traversal, the methane was injected inside the reactor to form
the hydrate. The reaction between water molecules and meth-
ane was a physical interaction. The hydrate formation reaction
equat ion might have been writt en as:
Figure 1. Schematic diagram of the spray reactor leading to hy-
drate formation.
In which B was the equilibrium gas to water molar ratio. The
constant for calculating the equations were based upon the
experimental data. As mentioned, in this model operating
cond ition were taken to be i so th ermal, h en ce on ly mass t ran s fer
during hydrate formation existed and respective calculations
were performed accordingly. The model parameters were of
geometrical dimensions and physical constants used in
developing the model [7].
In the present work, through solving equations involving hy-
drate formation, the theoretical data were calculated then com-
pared with experiment al ones .
3.1. Governing Equa tions
The distance travelled x(t) by water in reactor was calculated
from following correlation [7]:
24.41 0.093()
d xdx
dt dt
= −
The boundry conditions were:
t=0, at x=0 and v=v0
The constant of this correlation was calculated by MATLAB
software with model parameters related to hydrate formation
By water molecules travelling the horizontal distance thru the
reactor (x), the initial velocity decreased. Hence, the accelera-
tion subsequently lowered as well with the following equation:
aV t
= (2)
In which ht was the distance tra velled by the spr ay flow.
The diffusion coefficient of gas in water for hydrate
formation was calculated through the following eq uatio n:
8 0.5
7.410 ()
= (3)
where μw is t he associ ate factor of solvent (i .e.; water) and V
is the molar volume.
Mass transfer coefficient of methane in water during spray-
ing was provided by:
0.5 0.516
0.16 Re
KSc We
Supersaturation, Δμ, was the driving force for hydrate forma-
tion where it was the difference between the chemical poten-
tials of the old and new phases. For hydrate nucleation this
parameter should be Δμ=0 and for a single gas component sys-
tem such as methane it wa s calculat ed as follows:
( )
( )
rr er e
KT lnvPP
∆ =+∆−
When water mixed with the hydrate, a promoting chemical
was sprayed into the reactor and maintained at subzero tem-
peratures at which hydrate as well as; ice nucleations occurred
together. The n ucleation rate was determin ed as follows:
3 23
expexp exp()
h ef
 (6)
Copyright © 2012 SciRes. AMPC
where A is the kinetic parameter for nucleation. Vh is velocity
of hydrate and def is the effective surface ener gy.
The concentration of water, Cw(t), at any given time during
water injection could be determined from the following:
( )
( )
( )
() 1
dC t
tKe ttCtC
dt ++ =
In which, Ke is the varying rate constant used to determine
Cw. The moles of water crystallized, during semi-batch and
batch process might be calculated as:
For semi -batch period at t≤ ti:
() (())
w ww
M tCctQt
For batch period at t = ti:
( )()
( )1(()]
MtMtiKet tit ti=+− −
According to the above equations one might observe the
growth of water crystallized with time. Now, the moles of water
crystalli zed an d r emain ed as well as; t hat of th e gas far med in to
hydrate in vessel might be determined.
The relationship for moles of gas in hydrates at any time is
given by:
Water remaining in the system would be in the form of ice
the formation of which was inevitable in the spray reactor op-
eration due to the low temperature, where could be written as:
( )( )( )
MtMt Mt= −
( )
, is the initial moles of water in the system. So
the moles of gas remaining in the vessel are gi ven as:
( )()( )
MtMt Mt= −
( )
, is the tot al moles of meth ane in the system at
The gas to total water volume ratio, HFVF, or hydrate vol-
ume factor assuming the ideal gas law could be calculated as:
( )( )
MtRc P
= (13)
Details of all correlation and equation for hydrate formation
kinetics were presen ted in Ref. [7].
2. Results and Discussion
According to the Equation (1), the distance travelled by water
in vessel, X, was shown in Figure 2.
According to correlation (2), the hydrate acceleration, a, in
reactor with time decrea sed. The var iation s of accelerat ion with
time were showed in Figure 3.
The initial water in the system, Mw,i, at any given time was
presented in Figure 4.
The water crystallized into hydrate form, Mc,w, was calcu-
lated through the correlation (9) and shown in Figure 5. The
water re main ed in vessel was ice.
The mole fraction of methane in hydrate was about 0.2. The
equation (10), mole of methane in hydrate, Mgh, was displayed
in Figure 6:
The amount of gas in hydrate was indeed less than water
hence, the variation of remaining gas with time, Mgr, was also
low. This was calculated through the equation (11) and shown
in Figure 7.
Hydrate formation volume factor, HFVF, or the gas total
water volume ratio was determined from correlation (13) and
shown in Figure 8.
Figure 2. Variation of material’s travelled distance with time.
Figure 3. Materia l’s acc el er at i on va ri ation with time.
Figure 4. The initial mole of water injected variation with time.
Figure 5. The mole of water crystallized variation with time.
Co pyr i g ht © 2012 SciRes. AMPC
Figure 6. Variation of the mole of methane formed in the hydrate
with time.
Figure 7. Variation of the mole of remaining gas in the vessel with
Figure 8. The HFVF variation with time.
The error percentage in terms of absolute error between ex-
perimental and theoretical (or calculated) data generated from
the developed model was reported in Table 1 in order to con-
sider the accuracy of the hydrate formation model put together
in this r es ear ch.
It is seen through the above figures that at t = 798, due to
changes in the governing equations of hydrate formation lead-
ing to variations in spraying and stabilization periods, one
might see fractures in the behaviors displayed. Nonetheless; the
Table 1. The AAD and AE of effecting parameters.
Percentage of Error
Absolute Erro r
(%) AAD
(Experimental) AAD
Mwi 6.45 5.70 5 .37
Mwc 10.42 12.56 13.37
Mgr 0.9 0 0.19 0.20
Mgh 10.27 12.91 11.59
HFVF 6 .42 16.40 12.62
AAD (Average Absolute Deviation) and AE (Absolute Error)
values between theoretical and experimental extents of several
key affecting parameters displayed in Tabl e 1 revealed that the
accuracy of the developed model might be considered rather
4. Conclusions
The following behavioral patterns were demonstrated by this
When hydrate molecules traveled thru horizontal distance
of the react or, th eir aver age flight velocity increased while their
accelerat ion decreased.
The increase in the water injected showed an enhance-
ment in the hydrate formation because as mentioned, the high-
est volume of hydrate was related to th e water s pecies.
Increase in the stabilization period enhanced hydrate
amount formation.
During induction time period, hydrate formation occurred
and an exponential hydrate crystal growth followed.
The initial amount of water in the reactor increased with
time since the most important component of the hydrate was
indeed the water. In other words, not only the mole fraction of
this species in the hydrate was 80% but also, it was injected
into the reacto r wit h passage of time.
As time went by, the moles of methane in system de-
creased rather slowly due to the low initial consumption (i.e.;
about 5% of the total initial moles) of this species
All of these issues were indicative o f ho w the ch emistry and
physics of the hydrate material affected its displayed behavior.
This model paved down the road toward further optimization of
hydrate formation process and its applications which are cur-
rently undertaken in this laboratory.
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