chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

Experimental study of natural gas hydrates and a novel use

of neural network to predict hydrate formation conditions
Mohammad Ghavipour a, , Mina Ghavipour b , Minoo Chitsazan a , Seyed Hessam Najibi a ,
Saeed Shiry Ghidary b
a
b

Gas Engineering Department, Petroleum University of Technology, 63431 Ahwaz, Iran

Computer Engineering & Information Technology Department, Amirkabir University of Technology, 15875-4413 Tehran, Iran

a b s t r a c t
A novel high-pressure apparatus with various abilities in hydrate investigation elds has been designed, constructed
and fully described in the present paper. In order to achieve an appropriate understanding of the gas hydrate behavior
in formation and destabilization, series of laboratory experiments with six different gas mixtures were done and more
than 130 hydrate equilibrium points in the pressure range of about 4503000 psia were recorded. Different methods
of hydrate formation prediction were discussed and nally the new promising neural networks method was used.
Because of the previous works defects in accurate hydrate formation prediction via neural networks, a new use of
neural networks was introduced. Testing and validation of the new neural networks method indicates that it is a
reliable technique for the accurate prediction of hydrate formation conditions for generalized gas systems and can
be used in future automatic inhibitor dosing devices.
2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Hydrate formation; Natural gas; Neural network; Prediction; Experimental study

1.

Introduction

1.1.

What is hydrate?

Gas hydrates are kinds of clathrates discovered rstly by Davy

in 1810. A clathrate is any compound wherein guest molecules
are entrapped in a cage structure which is composed of host
molecules. Gas hydrates are crystalline solids that are formed
at low temperatures and normally high pressures at the presence of water and suitable size gas molecules (GPSA, 2004). The
gas molecules are captured in a cage-like structure produced
as a result of a network of hydrogen-bonded water molecules
(Byk and Fomina, 1968; Koh, 2002; Maddox and Erbar, 1992;
Sloan and Koh, 2008).
The gas hydrates are considered as undesirable solids
when they form in oil and gas transportation and processing equipments. They can cause detrimental obstacles to
the ow of oil and gas, serious damages to instruments and
fatal perils to eld workers because of high pressure pipeline
explosion and acid gases emission (Barker and Gomez, 1989;

Hammerschmidt, 1934; Sum et al., 2009). In these cases,

hydrate formation can be prevented by dehydrating the gas or
liquid, by maintaining temperature and/or pressure outside
the hydrate formation region or by injection of thermodynamic inhibitors or low dosage hydrate inhibitors (LDHIs).
On the contrary, gas hydrates can be applied in usable ways.
Gas transportation and storage (Berner, 1992; Fitzgerald, 2001;
Javanmardi et al., 2005, 2007; Jeon et al., 2006; Kerr, 2004;
Nogami et al., 2008), a promising and sustainable energy
resource (Collet and Kuuskraa, 1998; Makogon et al., 2007; Max
et al., 2006; Milkov and Sassen, 2002), water sweetening and
wastewater treating (Javanmardi and Moshfeghian, 2003), separation and purication of gas mixtures (Kang and Lee, 2000;
Lee, 2009; Ma, 2001), refrigeration and air conditioning systems
(Fournaison et al., 2004; Ogawa et al., 2006), and reducing green
house gases emission (House et al., 2006; Kang and Lee, 2000;
Lee, 2003). A detailed literature review on positive applications of gas hydrates can be found elsewhere (Eslamimanesh
et al., 2012; Englezos and Lee, 2005; Englezos, 1993; Chatti et al.,
2005).

Corresponding author. Tel.: +98 9371048445; fax: +98 6115550868.

E-mail addresses: Ghavipour@put.ac.ir, M.Ghavipour@gmail.com (M. Ghavipour), Mina ghavipour@aut.ac.ir (M. Ghavipour),
M.chitsazaaan@gmail.com (M. Chitsazan), Najibi@put.ac.ir (S.H. Najibi), Shiry@ce.aut.ac.ir (S.S. Ghidary).
Received 2 November 2011; Received in revised form 26 July 2012; Accepted 13 August 2012
0263-8762/$ see front matter 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2012.08.010

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

1.2.2 Second method is using gas-gravity plots developed by

Katz (1945). These plots are in two forms: rstly, plots
that relate the hydrate formation pressure and temperature to gas gravity dened as the apparent molecular
weight of a gas mixture divided by that of air and secondly, the charts of permissible expansion that a natural
gas can undergo without risk of hydrate formation.

Nomenclature
bj
ci
E
Kvs
ni
oj
Pi
Pt
ti
wji
xs

xi
yi

1.2.
(HFP)

threshold value which is belong to neuron j

network predicted output for training example
i
mean square error (MSE)
vaporsolid equilibrium constant
mole number of component i to make a special
gas mixture
value which is calculated by neuron j
the cell pressure after injecting pure gas component i
the total pressure of the gas mixture in the cell
target output for training example i
weight of the connection from neuron i to neuron j
mole fraction of the ith hydrocarbon component in the solid phase considered on a
water-free basis
output value from neuron i
mole fraction of the ith hydrocarbon component in the gas phase considered on a
water-free basis

These methods are simple graphical techniques that may

be useful for an initial estimate of hydrate formation conditions and rough design of valves and chokes. Sloan (1984) by
statistical accuracy analysis has reported that these methods
are not accurate enough and for the same gas gravity with different mixtures may lead to signicant error in the predicted
values.
1.2.3 Empirical correlations that are developed in different
forms and with various number of parameters (Holder
et al., 1988; Makogon, 1981).
1.2.4 method is based on a statistical thermodynamic
approach developed by Van der Waals and Platteeuw
(1959). This approach accounts for the interactions
between gas molecules and water molecules forming
the crystal lattice.

Hydrate formation (or dissociation) prediction

The importance of the accurate hydrate formation (or dissociation) prediction is evident because of its wide applications
(such as determination of the limits for natural gas expansion during throttling in valves, chokes and restrictions, the
amount of inhibitor to be injected and so on), and because
experimental measurements of hydrate formation (or dissociation) conditions for every specic gas composition and every
pressure are impractical.
Several methods are useful for predicting hydrate formation of gases; however, each one has some limitations
in pressure and temperature range or in gas constituents.
Neglecting any of these limitations will cause serious inaccuracy. These correlations and methods can be classied into
four major groups (GPSA, 2004; Maddox and Erbar, 1992).
1.2.1 Katz method that uses vaporsolid equilibrium constants to nd hydrate formation (or dissociation)
temperature or pressure (Carson and Katz, 1942). The
calculation is iterative and convergence is achieved
when the following objective function is satised:
n

yi
i=1

Kvs

= 1.0 and Kvs =

y
xs

265

(1)

In calculations, nitrogen and all molecules too large to

form hydrates (for example hydrocarbons larger than normal
butane) have a K-value of innity. Katz correlation is not recommended above 10001500 psia, depending on composition.
Prediction of hydrate formation conditions at higher pressures
requires the use of other methods. Sloan (1989) presents an
alternative set of Kvs values which are dependent upon gas
composition and type of hydrate structure and are valid up to
4000 psia.

In recent studies, it is attempted to modify and validate

above method for other constituents such as inhibitors and to
improve its predictive accuracy by modifying its parameters
(Dharmawardhana et al., 1980; John et al., 1985; Mehta and
Sloan, 1994; Nagata and Kobayashi, 1966; Ng and Robinson,
1976; Tohidi et al., 1996). Accuracy and limitations of this
method have been discussed by Sloan (1991). For multicomponent systems, an average error of 25% may be expected
in hydrate dissociation pressure prediction.
Some of the correlations mentioned above are not accurate
enough and most of the times consider only simple pure gases
and their mixtures. In addition, some of these correlations are
presented originally in graphical form, thus making it difcult
to use them within general computer packages for simulation
and design. Thus it is obvious that there is a research need for
developing a new model. This model should give high accuracy, should be reliable and less sensitive to noisy input data
and can be continuously retrained and got matched to new
inputoutput data.
Recently, it has been seen an explosion of interest in the use
of articial neural networks, mainly because of their ability to
handle complex and nonlinear problems in areas as diverse
as nance, medicine, engineering, geology, physics and biology (Basheer and Hajmeer, 2000; Ferentinos, 2005; Paliwal and
Kumar, 2009; Widrow et al., 1994). Articial neural networks
can be taught to learn correlative patterns between variables
and can be used subsequently to predict outputs from new
inputs. In petroleum engineering, neural networks have been
used to predict phase equilibria (Lee and Chen, 1993) and PVT
properties (Habiballah et al., 1996). Also neural networks have
been utilized recently to predict hydrate formation temperature and hydrate inhibition. In some works specic gravity
and one of temperature or pressure were used to predict
the hydrate formation condition (Elgibaly and Elkamel, 1999;
Heydari et al., 2006; Zahedi et al., 2009). Using specic gravity of gas sample as the input variable and neglecting the
gas components is not accurate because different compounds;
even with the same specic gravities; show different behaviors

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chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

Fig. 1 Schematic diagram of the constructed apparatus.

in hydrate formation. In some other works, gas compositions were used instead of gas specic gravities as the input
variable. Chapoy et al. (2007) employed a feed-forward articial neural network with 19 input variables (temperature, gas
hydrate structure, gas composition and inhibitor concentration in aqueous phase) and 35 neurons in single hidden layer
for estimating hydrate dissociation pressures of natural gases
in the presence/absence of inhibitor aqueous solutions. Their
model was trained using 3296 data gathered from the literature. They did not examine different numbers of hidden layers
and neurons to nd the optimum structure of their neural network. In the present work a new approach based on initial
gas composition and Leave-one-out method has been used,
different structures were examined and the results of the optimum structure have been compared to the former method (i.e.
specic gravity method).
The ultimate goal of entering computer-based methods in
hydrate formation prediction is to design a hydrate inhibition package that with known properties of owing gas (i.e.
gas composition, pressure and ow rate) and minimum temperature of the weather during a day can calculate and inject
the required amount of inhibitor to prevent hydrates to form.
This will lead us to construct unique inhibitor dosing devices
for accurate hydrate prevention and to minimize the cost of
inhibitors consumption.
In this paper, at rst the apparatus is described in details,
it is followed by explanation of experimental hydrate formation determination approach and at the end, neural networks
utilization to predict hydrate formation temperature will be
discussed.

2.

Materials and methods

2.1.

Apparatus description

A new apparatus was designed and constructed for gas

hydrate investigation with the operating temperature range of
15180 F (10 to 80 C) and pressure up to 3500 psia (24 Mpa).
The main cell (i.e. hydrate formation reactor) consists of a circular viewing window as well as several sensors to monitor

and control the operating conditions. A schematic diagram of

the apparatus has been shown in Fig. 1. The reaction chamber
is a cylindrical cavity which is constructed of 316 stainless
steel and has a volume of 1.1 l. The cell has a lid which is
fastened via bolts and sealed with gasket. This lid has been
equipped with 6 high-pressure connections. Two of these connections are for two temperature probes (one in gas phase and
the other one in aqueous phase), one for the GC analysis, one
for pressure transmitter and the two others for uid injection
and vacuum creation in the cell.
For thermoregulation purposes, the cell is housed in a
jacket, enabling thermal uid to circulate around. The jacket
covers all sides of the cell except the top, while the top of the
cell has been insulated. A programmable refrigeration system
with temperature accuracy of 0.5 C, circulates a mixture of
water and ethylene glycol as a refrigerant through the jacket.
A magnetically driven impeller is placed in the cell to facilitate equilibrium between two phases. A vacuum pump is also
connected to the main cell, which serves for its evacuation
whenever it is wanted to change the gas mixture. The temperature inside the chamber is measured with two thermistors
with a temperature range of 22 to 176 F (30 to 80 C). Two
thermistors are used to monitor the temperatures of either
phases inside the cell and to ensure that both of them have
the same temperature. Otherwise, the rate of heating or cooling via the circulator slows down to supply enough time for
thermal equilibrium to happen. A pressure transmitter with
a sensitivity of 1 psi is installed on the cell lid to measure the
pressure. Also a computer is employed to record the prole of
temperature and pressure of the main cell versus time and for
gas chromatography data acquisition and analysis. A liquid
metering pump (i.e. reciprocating with single acting piston) is
available for water or any chemical inhibitor injection to the
cell with a maximum discharge pressure of 4500 psia and ow
rate range of 0.019.99 ml/min. A booster pump is also hired
to pressurize the gas samples up to 3500 psia.
For gas composition analysis, samples can be taken from
hydrate formation cell to a gas chromatograph. The chromatograph is a 7890A Agilant that is equipped with ame ionization
detector (FID) and HP-PLOT Q (0.32 mm inside diameter, 30 m

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

length, 20 m lm thickness) as the capillary column. The

analysis is performed at isothermal oven with temperature
of 150 C and helium as the carrier gas. Injector and detector
temperatures are the same (i.e. 200 C) and injection split ratio
is 20/1. Run time is 15 min for each sample analysis.
At higher impeller speeds, the liquid formed a vortex which
extended the gasliquid interfacial area and it has been proven
that initial hydrate formation rate increases with increasing gasliquid interfacial area (Turner et al., 2009). Therefore,
impeller speed was kept xed during all of our experiments.
All of the instruments units have been converted to English
units (especially temperature F and pressure psia).

2.2.
Gas mixtures preparing and hydrate formation
determination approach
Hydrate formation vessel was opened through the top lid and
any possible moisture or solid particles were cleaned. Then
the cell was closed and sealed via bolts and gaskets. A special
gas mixture was prepared via the following procedure:
2.2.1 Current temperature, the gas mixture composition and
the nal pressure is known, the gas mixture compressibility factor is calculated by proper mixing rule
and available correlations (Ahmed, 2000), and with the
known vessel volume, the total mole number and each
component moles are attained.
2.2.2 The nal gas mixture at the proper pressure is made by
injecting every pure constituent to the cell and reach
to a special pressure that supply the required moles of
that component at the nal mixture. As it can be seen in
Fig. 2, an algorithm was written to compute these pressures by trial and error. Now to make a gas mixture with
known compositions (i.e. yc1 , yc2 , yc3 , . . .) the cell should
be lled with pure methane to the pressure of P1 . Afterwards, pure ethane is added to attained P2 and other
components with the calculated nal pressures should
be superimposed to reach to the nal mixture.
To conrm the exact composition of the ultimate created
gas mixture, a sample of the gas was tested through the sampling line via the gas chromatograph.
200 ml of deionized water was added to the cell by the
metering pump after heating via the heat traced line which
was piped from the pump to the cell. Warming the water to
160 F will facilitate the gas saturation. The water occupied
nearly 20 vol.% of the cell. The approximate hydrate formation temperature of the gas mixture was read from GPSA
(2004) book (i.e. from the charts that depict hydrate formation temperature versus pressure at different gas specic
gravities), then the cell was cooled to 10 F higher than that
temperature. Afterwards, the temperature and pressure monitoring was started with isochoric cooling of the cell. With
the programmable circulator, the cell was chilled nearly 1 F
(exact value was 0.5 C) and was left for 1 h. The cell pressure
decreased due to the gas thermal contraction and somewhat
because of gas absorption into the aqueous phase. Cooling
was continued until a severe pressure drop as well as a slight
temperature rise was observed. A pressure drop of nearly
180 psi was gained in 1 h although during gas thermal contraction, pressure decreased about 20 psi per hour. These values
varied for different experiments but the ratios of these pressure drops (i.e. pressure dope during hydrate formation over
thermal contraction pressure drop) were always about 7.510.

267

This intense pressure drop corresponded to the formation of

hydrate particles at the vapor/liquid interface that could be
seen through the viewing window. The temperature decreased
gradually until no further pressure drop was observed. After
that, a smooth heating process was started with the rate of
1 F per 30 min. Hydrate dissociation is much more faster than
hydrate formation. Hence, exact hydrate dissociation point
can be determined contrary to the hydrate formation point
that happens at lower temperature and higher pressure. For
the elementary steps where the hydrates were heated without dissociation, no considerable pressure rise occurred, but
at higher temperatures hydrate dissociation took place and
the vessel pressure had an intense rise until it crossed the former pressure curve that belonged to gas thermal contraction.
Then the two pressure curves made a single line. The contact point was the hydrate equilibrium point in which hydrate
dissociation completed.
With the aid of the experiences that had been gained on
numerous experiments of hydrate formation, the initial vessel
pressures were adjusted in a way that in spite of the pressure
drops due to the thermal contraction, the hydrate equilibrium
pressures would be within the range of 4503000 psia. It was
attempted to nd 2025 equilibrium points in the above pressure range for every individual gas composition. Four different
gas compositions plus pure methane were used to create ve
distinct specic gravities from 0.553 to 0.843. Gas mixture
number 6 was used to test the nal neural network model.
Detailed characteristics of the gas mixtures have been listed
in Table 1. At the experiments for a special gas composition,
new samples of deionized water and gas mixture were used
after several runs to prevent hydrate formation being inuenced by any possible residual structures or gas composition
changes from previous experiments.

3.

Articial neural network

Articial neural networks (ANNs) are a form of articial intelligence which attempt to mimic the behavior of the human
brain and nervous system. ANNs provide a robust approach to
approximating real-valued, discrete-valued and vector-valued
target functions. Neural network advantages include: adaptive learning, self-organization, real time operation and fault
tolerance via redundant information coding.
As illustrated in Fig. 3a, an articial neural network consists of a collection of processing elements (neurons) that are
arranged in layers and transform a set of inputs to a set of
desired outputs. The neurons from each layer are linked to
all of the other neurons appearing in the next layer. All the
neurons are connected with different weights (wji ). At each
neuron, the weighted input values (xi ) are summed and a
threshold value (bj ) is added. Then a non-linear transfer function (f()) is applied to this linear combination of inputs to
produce the output of the neuron (oj ) (see Fig. 3b):
oj = f



wji xi + bj


(2)

The output of one neuron provides the input to the neurons in the next layer. Neural network employs a training
algorithm (e.g. back-propagation) to adjust its weights on the
presentation of a training data set and minimize the network
performance function. The default performance function for
neural networks is mean square error (MSE) which means the
average squared error between the network output values and

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chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

P1= yc1 * Pt (inial guess for the rst pressure)

P1 ,T are known, pure C1

calculate Z1

Z1 , V, T and nc1 are known

calculate P1new

If

NO
P1 = P1 (new) (set P1equal to P1new )

Abs (P1new -P1)<1psi

YES
P2= P1new (inial guess for the second pressure)

P2 , T , yc1 and yc2 are known

calculate Z2

Z2 , V, T and (nc1 + nc2) are known

calculate P2new

If

NO
P2 = P2 (new) (set P2equal to P2new )

Abs (P2new P2)<1psi

YES
P3= P2new (inial guess for the third pressure)

Connue to nd pressures of all pure components injecon

Fig. 2 Algorithm of making a gas mixture with known composition.
Table 1 Characteristics of the prepared gas mixtures.
Number of gas samples #
Gas mixture specic gravity
Components mole fraction 1%
Methane (C1 )
Ethane (C2 )
Propane (C3 )
Normal butane (n-C4 )

0.55
Mole%
100
0
0
0

0.60
Mole%
90
10
0
0

0.65
Mole%
80
20
0
0

0.75
Mole%
70
20
10
0

0.84
Mole%
60
25
10
5

0.75
Mole%
60
40
0
0

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chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

X1
Wj,1
X2

Xn
Input
layer

Ij

( )

oj

Wj,n
bj

Output
layer

Hidden
layers

(a)

(b)

Fig. 3 (a) Interconnection of the multilayer neural network. (b) A typical neuron j in the hidden layer.
the target values for these outputs, which can be shown by E
in the following formula:

E=

1
n

n


(ti ci )

(3)

i=1

where n is the number of training data, ti and oi are the

target output and calculated output for training example i,
respectively. Once the training phase of the model has been
successfully accomplished, the performance of the trained
model has to be validated using an independent testing set.

data of the present study were compared with the previous

published data (Deaton and Frost, 1946; McLeod and Campbell,
1961; Nakamura et al., 2003; Sloan and Koh, 2008; Verma, 1974).
Hydrate equilibrium data of ternary gas mixtures exactly the
same as present study, were not available but for the rst and
third samples the data were available and based on Fig. 5, the
comparison is satisfying. It should be mentioned that the published data for comparing to the third gas sample are from
McLeod and Campbell (1961) study with a gas mixture of 80.9%
methane and 19.1% ethane.

4.2.

4.

Results and discussion

4.1.

Experimental

Hydrate equilibrium points of the ve gas compositions (gas

samples from 1 to 5) have been depicted in Fig. 4. The obvious behavior of hydrate formation has been satised via the
trends of the equilibrium curves in this gure, i.e. as the temperature decreases, hydrates form in lower pressures and as it
is shown, in higher specic gravities at a constant pressure,
hydrates appear at higher temperatures. The experimental

Prediction via neural network

In the present study, to achieve the highest accuracy while

developing a neural network model, various architectures
and training functions have been attempted. Four training
functions of trainlm (LevenbergMarquardt backpropagation),
traingdx (gradient descent with momentum and adaptive
learning rate backpropagation), trainscg (scaled conjugate
gradient backpropagation) and trainoss (one-step secant backpropagation) were tested. The number of layers varied from 1
to 10 with 5, 10 and 15 neurons in each hidden layer whereas
the neurons in the rst and last layers were xed to receive

Fig. 4 Hydrate equilibrium points of the ve gas samples.

270

(a)

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

3500

literature

3000

Pressure (psi)

this work
2500
2000
1500
1000
500
0
30

40

50

60

70

Temperature( F)

Pressure (psi)

(b)

4000
3500

Literature

3000

this work

Fig. 6 Mean squared error of different training functions

versus number of layers.

2500
2000
1500
1000
500
0
50

60

70

80

Temperature( F)
Fig. 5 Comparison of the present study experimental data
with the previous published data. (a) First gas sample (pure
methane). (b) Third gas sample (80% methane and 20%
ethane).

input and deliver output, respectively. To train these networks, 70% of the experimental data were used and with
the remaining 30% data, networks performance was assessed.
Pressure and specic gravity of the gas mixture were dened
as input variables and networks estimated the hydrate formation temperature as the output variable. It is concluded
from Table 2 and Fig. 6 that among the four training functions,
trainlm as the network training function and among various

architectures, a two-hidden layer network with 10 neurons

in each hidden layer possess the minimum MSE as well as
highest accuracy. As an evidence to prove the above result,
good tting of neural network predictions to the experimental
values can be seen in Fig. 7.
Accurate predicted data in Fig. 7 may be signicantly
in error for compositions other than those used to derive
the charts. Inability of the above model with input variable
denition of gas sample specic gravity and pressure was
clear especially in the cases of two gas mixture with the
same specic gravity and different concentrations of the gas
constituents. For more accurate determination of hydrate formation conditions, another model should be developed. The
novel model utilizes gas components mole fraction and pressure to predict the hydrate formation temperature. Similar to
the former model, the new model was trained and tested with
70% and 30% of the experimental data respectively (see Fig. 8).
In the cases that the numbers of initial data are not enough
to train the network satisfyingly, so that the network cannot
predict exactly, Leave-one-out method can be employed. In
this method, we split the data set D of size n into n partitions
of size 1 such that, D = Q1 Q2 Qn and Qi Qj =  where
/ j.
Qi = {(xi , ti )} and Qj = {(xj , tj )} for i, j = 1, . . ., n and i =

Table 2 MSE values and optimum number of neurons for different neural network models.
Training function

Number
of layers
trainlm
Number of neurons
1
2
3
4
5
6
7
8
9
10

0
5
10,10
5,5,5
10,5,5,5
5,5,5,15,15
5,10,10,10,15,5
5,15,15,5,15,10,10
5,15,5,5,15,10,15,15
5,5,5,10,5,5,5,10,10

traingdx

trainscg

trainoss

MSE

Number of neurons

MSE

Number of neurons

MSE

3.3655
0.0420
0.0312
0.0566
0.0546
0.0602
0.0517
0.0433
0.0319
0.0333

0
15
10,15
10,10,10
15,15,15,10
10,15,15,10,5
10,15,15,15, 15,10
10,10,15,15,15,15,5
5,15,15,10,15,5,10,5
15,15,10,10,10,15,5,10,5

3.0856
3.1854
1.3213
1.2919
0.7761
0.3412
1.0027
0.7689
0.5708
0.7450

0
10
15,10
15,10,10
15,15,15,10
5,5,15,15,10
10,15,15,10,15,5
15,10,15,10,15,5,15
5,15,15,10,15, 15,10,5
5,5,10,10,10,10,10,15,10

3.2810
2.1621
0.7529
0.6315
0.7256
0.3S15
0.2431
0.1511
0.1018
0.1204

Number of neurons
0
10
15,5
5,10,10
15,15,15,5
5,10,10,15,10
5,15,15,15,15,15
5,10,5,15,15,15,5
5,15,15,15,10,15,10,5
5,15,15,5,5,10,15,15,5

MSE
2.2894
2.2333
1.2469
0.7400
0.4935
0.5289
0.4024
0.2188
0.2184
0.3198

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

Fig. 7 Fitting of experimental values and predicted values

via neural network (specic gravity model).

271

Fig. 9 Fitting of experimental values and predicted values

via neural network trained by Leave-one-out method
(compositional model).

Each partition Qi is used systematically for testing exactly

once whereas the remaining partitions (i.e. n 1 data) are used
for training. Mean square error (MSE) is calculated by Eq. (3)
with a modication that n is the whole number of examples
in the data set D. Experimental data as well as predicted values
with this method have been presented in Fig. 9.
With the aid of this method, calculated MSE has the value
of 0.0679 which apparently is higher than the former method
error (i.e. 0.0312) but in fact this MSE value has been attributed
to the deviation of all 130 predicted data, however the MSE of
the specic gravity method is only for 30% of the data. Hence,
it can be said that Leave-one-out method is more accurate.
To assess the applicability of the new model, gas sample
number 6 that has the same specic gravity as the gas sample
number 4, but with different ingredients, has been used. Seven
experimental points was found and two of them were used to
train the model and ve points to test it. As illustrated in Fig. 10
excellent consistency has been found between experimental

Fig. 10 Fitting of nal test experimental values and

predicted values via neural network trained by
Leave-one-out method (compositional model).
values and predicted values. This proves that compositional
model with Leave-one-out method has the ability of accurate
hydrate formation prediction for every gas mixture.

5.

Fig. 8 Fitting of experimental values and predicted values

via neural network (compositional model).

Conclusion

At the present work about 130 equilibrium points of hydrate

formation have been found as a result of almost 10 months
severe experimental work. These experimental data provide
an insight into the process of gas hydrates formation and
dissociation. Neural networks with two different structures
(denitions) of independent variables have been employed to
HFTP. Inability of the rst structure with gas sample specic
gravity and pressure as the input variables was clear especially
in the cases of two gas mixtures with the same specic gravity
and different concentrations of gas constituents. In the second

272

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

structure where pressure and components mole fraction of gas

mixture had been dened as the independent variables, more
accurate results were attained. To achieve the optimum neural
network model, various architectures and training functions
were attempted. Among various training functions, trainlm
as the network training function and among various architectures, a two-hidden layer network with 10 neurons in each
hidden layer showed the minimum MSE as well as highest accuracy. Finally, Leave-one-out method was introduced
and utilized to predict hydrate formation (or dissociation)
condition of several gas mixtures. From MSE measurements
of different methods, it was concluded that compositional
model using Leave-one-out method has the ability of accurate hydrate formation prediction for every gas mixture. These
ndings will lead us to use neural network as a precise and
reliable predictor for hydrate formation conditions.

References
Ahmed, T., 2000. Reservoir Engineering Handbook, second ed.
Gulf Publishing Company, Houston, TX.
Barker, J.W., Gomez, R.K., 1989. Formation of hydrates during
deepwater drilling operations. J. Petrol. Technol. 41 (3),
297301.
Basheer, I.A., Hajmeer, M., 2000. Articial neural networks:
fundamentals, computing, design, and application. J.
Microbiol. Methods 43, 331.
Berner, D., 1992. The marine transport of natural gas in hydrate
form. In: Proc. Second Int. Offshore Polar Eng. Conf., San
Francisco, pp. 636643.
Byk, S.S., Fomina, V.J., 1968. Gas hydrates. Russ. Chem. Rev. 37 (6),
469491.
Carson, D.B., Katz, D.L., 1942. Natural gas hydrates. Trans. AIME,
146150.
Chapoy, A., Mohammadi, A.H., Richon, D., 2007. Predicting the
hydrate stability zones of natural gases using articial neural
networks. Oil Gas Sci. Technol. 62 (5), 701706.
Chatti, I., Delahaye, A., Fournaison, L., Petitet, J., 2005. Benets
and drawbacks of clathrate hydrates: a review of their areas of
interest. Energy Convers. Manage. 46, 13331343.
Collet, T., Kuuskraa, V., 1998. Hydrates contain vast store of world
gas resources. Oil Gas J. 96 (19), 9095.
Deaton, W.M., Frost Jr., E.M., 1946. Gas Hydrates and their
Relation to the Operation of Natural-Gas Pipe Lines, U.S.
Bureau of Mines Monograph.
Dharmawardhana, P.B., Parrish, W.R., Sloan, E.D., 1980.
Experimental thermodynamic parameters for the prediction
of natural gas hydrate dissociation conditions. Ind. Eng.
Chem. Fundam. 19 (4), 410414.
Elgibaly, A., Elkamel, A., 1999. Optimal hydrate inhibition policies
with the aid of neural networks. Energy Fuels 13, 105113.
Englezos, P., Lee, J.D., 2005. Gas hydrates: a cleaner source of
energy and opportunity for innovative technologies. Korean J.
Chem. Eng. 22 (5), 671681.
Englezos, C.P., 1993. Clathrate hydrates. Ind. Eng. Chem. Res. 32,
12511274.
Eslamimanesh, A., Mohammadi, A.H., Richon, D., Naidoo, P.,
Ramjugernath, D., 2012. Application of gas hydrate formation
in separation processes. A review of experimental studies. J.
Chem. Thermodyn. 46, 6271.
Ferentinos, K.P., 2005. Biological engineering applications of
feedforward neural networks designed and parameterized by
genetic algorithms. Neural Netw. 18, 934950.
Fitzgerald, A., 2001. Offshore gas-to-solids technology. SPE 71805.
Fournaison, L., Delahaye, A., Chatti, I., Petitet, J.P., 2004. CO2
hydrates in refrigeration processes. Ind. Eng. Chem. Res. 43
(20), 65216526.
Gas Processors Suppliers Association, 2004. GPSA Engineering
Data Book, twelfth ed. Gas Processors Association, Oklaoma.

Habiballah, W.A., Startzman, R.A., Barrufet, M.A., 1996. Use of

neural networks for prediction of vapor/liquid equilibrium K
values for light-hydrocarbon mixtures. SPERE, 121126.
Hammerschmidt, E., 1934. Formation of gas hydrates in natural
gas transmission lines. Ind. Eng. Chem. 26 (8), 851855.
Heydari, A., Shayesteh, Sh., Kamalzadeh, K., 2006. Prediction of
hydrate formation temperature for natural gas using articial
neural network. Oil and Gas Business, Electron. Sci. J. (2),
14.07.06.
Holder, G.D., Zetts, S.P., Pradhan, N., 1988. Phase behavior in
systems containing clathrate hydrates. Rev. Chem. Eng. 5 (1),
170.
House, K.Z., Schrag, D.P., Harvey, C.F., Lackner, K.S., 2006.
Permanent carbon dioxide storage in deep-sea sediments.
Proc. Natl. Acad. Sci. U.S.A. 103 (33), 1229112295.
Javanmardi, J., Moshfeghian, M., 2003. Energy consumption and
economic evaluation of water desalination by hydrate
phenomenon. Appl. Therm. Eng. 23 (7), 845857.
Javanmardi, J., Nasrifar Kh Najibi, S.H., Moshfeghian, M., 2007.
Natural gas transportation: NGH or LNG? World Rev. Sci.
Technol. Sustain Dev. 4 (2/3), 258267.
Javanmardi, J., Nasrifar Kh Najibi, S.H., Moshfeghian, M., 2005.
Economic evaluation of natural gas hydrate as an alternative
for natural gas transportation. J. Appl. Therm. Eng. 25,
17081723.
Jeon, Y.H., Kim, N.J., Chun, W.G., Lim, S.H., Kim, C.B., Hur, B.K.,
2006. A study of the kinetics characteristics of natural gas
hydrate. J. Ind. Eng. Chem. 12 (5), 733738.
John, V.T., Papadopoulos, K.D., Holder, G.D., 1985. A generalized
model for predicting equilibrium conditions for gas hydrates.
AIChE J. 31 (2), 252259.
Kang, S.P., Lee, H., 2000. Recovery of CO2 from fuel gas using gas
hydrate: thermodynamic verication through phase
equilibrium measurements. Environ. Sci Technol. 34 (20),
43974400.
Katz, D.L., 1945. Predictions of conditions for hydrate formation
in natural gases. Trans. AIME 160, 140144.
Kerr, R.A., 2004. Energy-gas hydrate resource: smaller but sooner.
Science (Washington, DC, USA) 303 (5660), 946947.
Koh, C.A., 2002. Towards a fundamental understanding of natural
gas hydrates. Chem. Soc. Rev. 31 (3), 157167.
Lee, H.J., 2009. Gas hydrates formation process for
pre-combustion capture of carbon dioxide. Energy 35 (6),
27292733.
Lee, S., 2003. CO2 hydrate composite for ocean carbon
sequestration. Environ. Sci. Technol. 37 (16), 37013708.
Lee, M.J., Chen, J.T., 1993. Fluid property prediction with the aid of
neural networks. Ind. Eng. Chem. Res. 32, 995997.
Ma, C.F., 2001. Separation of Gas Mixtures using Hydrate
Technology. Ph.D. Thesis. University of Petroleum, Beijing.
Maddox, R.N., Erbar, J.D., 1992. Gas Conditioning and Processing,
vol. 1., seventh ed. Campbell Petroleum Series, Oklaoma.
Makogon, Y.F., 1981. Hydrates of Natural Gas. PennWell, Nedra,
Moscow.
Makogon, Y., Holditch, S., Makogon, T., 2007. Natural
gas-hydratesa potential energy source for the 21st century.
J. Petrol. Sci. Eng. 56 (13), 1431.
Max, M., Johnson, A., Dillon, W., 2006. Economic Geology of
Natural Gas Hydrate. Springer, Dordrecht, the Netherlands.
McLeod, H.O., Campbell, J.M., 1961. Natural gas hydrates at
pressures to 10000 psia. J. Petrol. Technol. 222, 590594.
Mehta, A.P., Sloan, E.D., 1994. A thermodynamic model for
structure-H hydrates. AIChE J. 40 (2), 312320.
Milkov, A., Sassen, R., 2002. Economic geology of offshore gas
hydrates accumulations and provinces. Mar. Petrol. Geol. 19
(1), 111.
Nagata, I., Kobayashi, R., 1966. Predictions of dissociation
pressures of mixed gas hydrates from data for hydrates of
pure gases with water. Ind. Eng. Chem. Fundam. 5 (6), 466469.
Nakamura, T., Makino, T., Sugahara, T., Ohgaki, K., 2003. Stability
boundaries of gas hydrates helped by methane structureH
hydrates of methylcyclohexane and
cis-1,2-dimethylcyclohexane. Chem. Eng. Sci. 58, 269273.

chemical engineering research and design 9 1 ( 2 0 1 3 ) 264273

Ng, H.J., Robinson, D.B., 1976. The measurement and prediction of

hydrate formation in liquid hydrocarbonwater system. Ind.
Eng. Chem. Fundam. 15 (4), 293298.
Nogami, T., Oya, N., Ishida, H., Matsumoto, H., 2008. Development
of natural gas ocean transportation chain by means of natural
gas hydrate (NGH). In: Proc. 6th Int. Conf. Gas Hydrates (ICGH),
British Columbia, Vancouver, Canada.
Ogawa, T., Ito, T., Watanabe, K., Tahara, K., Hiraoka, R., Ochiai, J.,
et al., 2006. Development of a novel hydrate-based
refrigeration system: a preliminary overview. Appl. Therm.
Eng. 26 (1718), 21572167.
Paliwal, M., Kumar, U.A., 2009. Neural networks and statistical
techniques. A review of applications. Expert Syst. Appl. 36,
217.
Sloan, E.D., 1989. Vaporsolid equilibrium ratios for structure I &
II natural gas hydrates. In: Proc. 60th GPA Annu. Conv., San
Antonio, TX.
Sloan, E.D., 1984. Phase equilibrium of natural gas hydrates. In:
Proc. 63rd GPA Conv, pp. 163169.
Sloan, E.D., Koh, C.A., 2008. Clathrate Hydrates of Natural Gases,
third ed. Taylor and Francis/Group CRC Press.
Sloan, E.D., 1991. Clathrate Hydrates of Natural Gases. Marcel
Dekker, New York.

273

Sum, A.K., Koh, C.A., Sloan, E.D., 2009. Clathrate hydrates: from
laboratory science to engineering practice. Ind. Eng. Chem.
Res. 48 (16), 74577465.
Tohidi, B., Danesh, A., Todd, A.C., Burgass, R.W., 1996.
Measurement and prediction of hydrate-phase equilibria for
reservoir uids. SPE Prod. Facil. 11 (2), 6976.
Turner, D.J., Miller, K.T., Sloan, E.D., 2009. Methane hydrate
formation and an inward growing shell model in water-in-oil
dispersions. Chem. Eng. Sci. 64, 39964004.
Van der Waals, J.H., Platteeuw, J.C., 1959. Clathrate solutions. Adv.
Chem. Phys. 11, 157.
Verma, V.K., 1974. Gas Hydrates from Liquid HydrocarbonWater
Systems. Ph.D. Thesis. University of Michigan, University
Microlms No. 75-10,324, Ann Arbor, MI.
Widrow, B., Rumelhart, D.E., Lehr, M.A., 1994. Neural networks:
applications in industry, business and science. Commun. ACM
37 (3), 93105.
Zahedi, G., Karami, Z., Yaghoobi, H., 2009. Prediction of hydrate
formation temperature by both statistical models and
articial neural network approaches. Energy Convers.
Manage. 50, 20522059.