BELLOUM Mohamed
Laboratory of Materials Chemistry
Department of Chemistry
Faculty of Science
University of Batna, 05 avenue chahid boukhlouf
05000 Batna, Algeria
Email: mbelloum@voila.fr
OTMANINE Ghazi
Laboratory of Hydrocarbons technology
Department of Chemistry
Faculty of Hydrocarbons & Chemistry
University of Boumerdes, Avenue of
independence, 35000 Boumerdes, Algeria
Email: oth_gha@yahoo.fr
ABSTRACT
NOMENCLATURE
During field exploitation or in the expedition lines or even
during its handling process, natural gas is in permanent contact
with an aqueous phase. Under certain pressure and temperature
conditions, crystal deposits like ice are formed. These deposits,
commonly called hydrates, are considered as a nuisance which
can generate plugs, or even damage gas processing equipments
causing total shutdowns sometimes with fatalities.
A new field of gas condensate recently discovered in south
of Algeria caused a lot of difficulties and even accidents during
its operation due to hydrates formation. This is why identifying
the conditions of gas hydrates formation in this field and
possible solutions to prevent their formation have become
imperative. For this purpose, we took this real case which is
within the framework of a laboratory concrete study to identify
the hydrate formation and stability conditions (P,T)
experimentally, and identify curves which by identifying
integrity zones for operators to work outside these conditions,
and the influence of inhibitors on the prevention of hydrates.
Our approach is to reconstitute reservoir fluid by mean of
recombination of two validated separator liquid and gas
samples, by carrying out a PVT study of both fluids and
measuring the conditions of hydrate formation. In addition, a
numerical study was performed using PVTsim commercial
software, used to predict hydrate formation conditions and the
impact of inhibitors.
KEY WORDS
Hydrates, condensate gas, plug, PVT, safety
Vl : Liquid volume
M i : Mass molar of component i in the gas mixture
INTRODUCTION
Hydrates belong to the class of clathrates, which are
inclusion compounds. The "clathrate" word was used the first
time by Powell in 1948, and derived from the Latin word
"clathratus" which means "in capping". Clathrates are solid
crystallized in which some atoms or molecules are trapped in
cages provided by the assembly of another type of molecules.
When the crystal lattice is formed by water molecules linked
together by hydrogen bonds and the cavities are occupied by
gaseous molecules, the formed clathrates are called hydrates.
[1].
The most common gas hydrates morphology is methane
hydrate (Fig.1). There are other gas molecules including ethane,
propane, butane, isobutane, pentane, nitrogen, carbon dioxide
and hydrogen sulfide.
show an accident during the well flow back test). This is why
identifying the conditions of gas hydrates formation in this field
and possible solutions to prevent their formation have become
imperative.
To clearly define the hydrates, predict their equilibrium
conditions and determine the relationship between pressure and
temperature under which those hydrates form and dissociate,
equilibrium curves were used. These curves can be generated
by a series of laboratory experiments, or are more commonly
conducted using thermodynamic software such as PVTsim
based on the hydrocarbons composition and aqueous phases in
the system [9, 10].
.
Picture-1: hydrate plug
formed in the pipeline
Picture-3: destroyed
pipeline
Picture-4: damaged
pipeline
SAMPLING METHODS
Two sampling methods are applied today; downhole
sampling and surface sampling [11, 12, 13, 14]. The first
method is applied in the case of a single-phase effluent. The
second one is much applied in the case of natural gas. In the
case of gas with condensate leading to the production of a twophase effluent, sampling is performed at high pressure separator
by taking gas sample (separator gas) and liquid sample
(separator liquid).
SAMPLES VALIDATION
For the separator liquid, we should first determine bottles
opening pressure and saturation pressure at the separation
temperature, which must be identical to the separation pressure.
Since our gas is a condensate gas, we should determine the
saturation pressure of the separator liquid which is performed
m pv
. (1.4)
V lt
( d .Z ) ch
( d .Z ) lab
GOR cha Fc
Yi M i
15
15 )
nl
ng
zi
nl xi
nl xi
n g yi
xi
n g yi
nl
(1.5)
nt
(nt ) z i
ng
ng
1 (
nl
ng
.. (1.6)
) yi
nl
.. (1.7)
Supposing
that a liquid volume V generates a gas volume Vg and a liquid
mass, we will get:
ng
Vg M l
nl
V mol
.. (1.8)
Vl
. (1.2)
ng
i 1
Mm
M air
xi
1 (
. (1.9)
GOR
zi
xi M i
V mol
. (1.3)
GOR
nl
GORlab
. (1.1)
V mol
GOR
V mol
xi M i
) yi
.. (1.10)
xi M i
l
EXPERIMENTAL SET-UP
1. SAMPLES VALIDATION
Sample N
Cylinder N
Separator
Pressure
(psig)
Separator
Temperature
(C)
Lab Opening
Pressure
(psig)
Lab Opening
Temperature
(C)
Separator Gas
1
2
CGS1
CGS2
270
270
39
39
268
260
39
39
Sample N
Cylinder N
Separator
Pressure
(psig)
Separator
Temperature
(C)
Lab Opening
Pressure
(psig)
Lab Opening
Temperature
(C)
Separator Liquid
1
2
CLS1
CLS1
270
270
39
39
270
260
39
39
CME TEST
1,800
1,650
1,350
1,200
1,050
0,900
1000
2000
3000
Pressure (psig)
1,500
28.014
44.010
16.043
30.070
44.097
58.124
58.124
72.151
72.151
86.178
96.000
107.00
121.00
134.00
147.00
161.00
175.00
190.00
206.00
222.00
237.00
251.00
263.00
275.00
291.00
305.00
318.00
331.00
345.00
359.00
374.00
388.00
402.00
580.00
1.17
1.59
81.35
10.31
3.54
0.49
0.86
0.27
0.23
0.13
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
N2
CO2
C1
C2
C3
iC4
nC4
iC5
nC5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30+
1,500
Total
Average Molar Mass "Mm" (g/mole)
Density "d" (air = 1)
1,350
100.00
20.05
0.692
1,050
0,900
400
900
1400
1900
2400
2900
3400
Pressure (psig)
1
2
average
848.93
848.63
(c
m pv
10.68
10.38
Vlt
14.90
14.50
(g/c
838.25
838.25
m pr
m3)
m pr
m pv
m)
(g)
Test N
(g)
0.717
0.716
0.7165
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30+
28.014
44.010
16.043
30.070
44.097
58.124
58.124
72.151
72.151
86.178
96.000
107.00
121.00
134.00
147.00
161.00
175.00
190.00
206.00
222.00
237.00
251.00
263.00
275.00
291.00
305.00
318.00
331.00
345.00
359.00
374.00
388.00
402.00
580.00
4.25
1.39
31.56
27.90
20.37
3.33
6.55
1.86
1.45
0.88
0.36
0.07
0.02
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.01
0.05
0.36
1.96
5.59
2.49
7.02
5.38
5.74
12.32
17.33
11.76
10.00
6.09
3.84
2.58
1.99
1.40
1.05
0.77
0.58
0.44
0.34
0.25
0.19
0.14
0.10
0.08
0.06
0.04
0.02
0.01
0.01
0.01
Total
100.00
N2
CO2
C1
C2
C3
iC4
nC4
iC5
nC5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
Liquid
flash
"xiMi"
28.014
44.010
16.043
30.070
44.097
58.124
58.124
72.151
72.151
86.178
96.000
107.00
121.00
134.00
147.00
161.00
175.00
190.00
206.00
222.00
0.18
0.02
9.96
7.79
4.15
0.11
0.43
0.03
0.02
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.02
0.06
0.59
2.47
1.44
4.08
3.88
4.14
10.62
16.63
12.58
12.10
8.16
5.65
4.15
3.48
2.67
2.16
1.72
0.69
0.26
5.33
6.09
7.95
2.62
6.95
4.82
5.06
10.50
14.63
9.90
8.41
5.12
3.23
2.17
1.67
1.18
0.88
0.65
0.49
0.37
0.29
0.21
0.16
0.12
0.08
0.07
0.05
0.03
0.02
0.01
0.01
0.01
Total
100.00
91.74
Components
N2
CO2
C1
C2
C3
iC4
nC4
iC5
nC5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30+
1.38
1.10
0.91
0.69
0.55
0.44
0.30
0.28
0.21
0.13
0.09
0.05
0.05
0.07
100.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Components
237.00
251.00
263.00
275.00
291.00
305.00
318.00
331.00
345.00
359.00
374.00
388.00
402.00
580.00
Separator Gas
Molar
Composition
(%)
Separator
Liquid
Molar
Composition
(%)
Reservoir fluid
Molar
Composition (%)
28.014
44.010
16.043
30.070
44.097
58.124
58.124
72.151
72.151
86.178
96.000
107.00
121.00
134.00
147.00
161.00
175.00
190.00
206.00
222.00
237.00
251.00
263.00
275.00
291.00
305.00
318.00
331.00
345.00
359.00
374.00
388.00
402.00
580.00
1.17
1.59
81.35
10.31
3.54
0.49
0.86
0.27
0.23
0.13
0.06
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.69
0.26
5.33
6.09
7.95
2.62
6.95
4.82
5.06
10.50
14.63
9.90
8.41
5.12
3.23
2.17
1.67
1.18
0.88
0.65
0.49
0.37
0.29
0.21
0.16
0.12
0.08
0.07
0.05
0.03
0.02
0.01
0.01
0.01
1.16
1.55
79.07
10.18
3.67
0.55
1.04
0.41
0.38
0.44
0.50
0.30
0.25
0.15
0.10
0.07
0.05
0.04
0.03
0.02
0.02
0.01
0.01
0.01
0.01
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
100.00
100.00
100.00
20.05
91.74
22.21
Total
Average Molar Mass "Mm"
(g/mole)
5000
4500
4000
3500
(a)
(c)
(b)
(d)
Pressure (psig)
Unsafe region
(hydrate zone)
3000
2500
2000
1500
Safe region
(no hydrate)
1000
500
0
10
15
25
30
4500
4000
Pressure (psig)
20
Temperature (C)
3000
2500
Unsafe region
(hydrate zone)
2000
1500
1000
Safe region
(no hydrate)
500
0
-10
-5
10
15
20
25
30
Temperature (C)
5000
0% vol de DEG
4500
4000
3500
Pressure (psig)
3000
2500
2000
1500
1000
500
0
5000
0% vol methanol
4500
10
15
25
30
3500
20
Temperature (C)
4000
Pressure (psig)
3000
2500
COMPARATIVE STUDY
2000
1500
1000
500
0
-10
-5
10
15
20
25
30
Temperature (C)
4000
Pressure (psig)
3500
F ( P,V , T , X )
0% vol TEG
4500
3000
2500
2000
1500
1000
500
0
0
10
15
20
25
30
Temperature (C)
5000
Model (PVT sim)
4500
Experiment
4000
2 5% vo l M eOH_ PVTs im
50 % vo lM eOH_ PVTs im
5000
4500
3500
4000
3000
3500
Pressure (psig)
Pressure (psig)
0 % vo l M eOH_ PVTs im
2500
2000
1500
1000
3000
2500
2000
1500
1000
500
500
0
0
10
15
20
25
-15
30
-5
15
25
35
Temprature (C)
Temperature (C)
5% vo l wa te r s e p_P VTs im
5000
5% vo l s e p wa te r_Expe rime nt
2 5% vo l TEG_ PVTs im
50 % vo l TEG_ PVTs im
4500
5000
4000
4500
3500
3000
4000
2500
3500
Pressure (psig)
Pressure (psig)
0 % vo l TEG_ PVTs im
2000
1500
1000
500
3000
2500
2000
1500
0
10
12
14
16
18
20
22
24
26
28
1000
30
Temprature (C)
500
0
-10
-5
10
15
20
25
30
0 % vo l DEG_ PVTs im
2 5% vo l DEG_ PVTs im
50 % vo l DEG_ PVTs im
5000
4500
4000
Pressure (psig)
3500
3000
2500
2000
1500
1000
500
0
-10
10
20
30
REFERENCES
[1] M. M Mooijer van den Heave, Phase Behaviour and
Structural Aspects of Ternary Casthrate Hydrates Systems,
these of doctorat: Technische Universiteit Delft (2004).
[2] E. Berecz, M. Bella-achs, Gas Hydrates, Edition Elsevier
(1983).
[3] A. Rojey, Le Gaz Naturel, Production, Traitement et
Transport, Editions Technip, Paris, France (1994).
[4] Y. H. Jeaon, N. J. Kim, W. G. Chum, S.H. Lim, C. B. Kim,
and B. K. Hur, A Study of the Kinetic Characteristics of
Natural Gas Hydrate, Ind. Eng. Chem, Vol. 12, N. 5, p.
733-738 (2006).
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