Journal of Natural Gas Chemistry 18(2009)

A novel correlation for estimation of hydrate forming

condition of natural gases
Alireza Bahadori

, Hari. B. Vuthaluru
Department of Chemical Engineering, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia
[ Received April 20, 2009; Revised May 13, 2009; Available online , 2009 ]
Abstract
An inherent problem with natural gas production or transmission is the formation of gas hydrates, which can lead to safety hazards to produc-
tion/transportation systems and to substantial economic risks. Therefore, an understanding of conditions where hydrates form is necessary to
overcome hydrate related issues. Over the years, several models requiring more complicated and longer computations have been proposed for
the prediction of hydrate formation conditions of natural gases. For these reasons, it is essential to develop a reliable and simple-to-use method
for oil and gas practitioners. The purpose of this study is to formulate a novel empirical correlation for rapid estimation of hydrate formation
condition of sweet natural gases. The developed correlation holds for wide range of temperatures (265 298 K), pressures (1200 to 40000 kPa)
and molecular weights (1629). New proposed correlation shows consistently accurate results across proposed pressure, temperature and
molecular weight ranges. This consistency could not be matched by any of the widely accepted existing correlations within the investigated
range. For all conditions, new correlation showed average absolute deviation to be less than 0.2% and provided much better results than the
widely accepted existing correlations.
Key words
gas hydrate; correlation; natural gas
1. Introduction
A gas hydrate is an ice-like crystalline solid called a
clathrate, which occurs when water molecules form a cage-
like structure around smaller guest molecules. The most com-
mon guest molecules are methane, ethane, propane, isobutane,
normal butane, nitrogen, carbon dioxide, and hydrogen sulfide
[1,2]. It should be noted that normal butane does form a hy-
drate, but is very unstable [3]. It has been assumed that normal
paraffin molecules larger than normal butane are nonhydrate
formers [4,5]. While many factors influence hydrate forma-
tion, the two major conditions that promote hydrate formation
are (1) the gas being at the appropriate temperature and pres-
sure, and (2) the gas being at or below its water dew point.
Other factors that affect hydrate formation include mixing,
kinetics, type of physical site, surface for crystal formation,
agglomeration and the salinity of the system.
For the optimal design of gas production systems, it is im-
perative that hydrate formation can be adequately predicted.
There are numerous methods available for predicting hydrate
formation conditions in natural gas systems. The most reliable
of these models requires a gas analysis. However, if the gas
composition is not known, even the previous methods can-
not be used to predict the hydrate formation conditions, and
the Katz (1945) gravity chart [6] can be used to predict the
approximate pressure and temperature for hydrate formation.
Therefore, there is an essential need to develop a simple-to-
use method for appropriate prediction of hydrate formation
conditions of natural gases.
2. Methodology to develop new correlation
The required data to develop this correlation includes the
reported data for hydrate formation condition of natural gases
as well as temperature and pressure. In this work, the hy-
drate formation condition is predicted rapidly by proposing a
novel correlation, which has been developed, based on newly
proposed numerical model [7,8]. The following methodology
has been applied to develop this correlation.
Firstly, hydrate formation temperatures are correlated as a
function of pressure for various molecular weights. Then, the
calculated coefficients for these polynomials are correlated as
a function of molecular weight. The derived polynomials are
applied to calculate new coefficients for Equations (1) and (2)

Corresponding author. Tel: +61 8 9266 1782; Fax: +61 8 9266 2681; E-mail: Alireza.bahadori@postgrad.curtin.edu.au
Copyright2009, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. All rights reserved.
doi:10.1016/S1003-9953(08)60143-7
2 Alireza Bahadori et al./ Journal of Natural Gas Chemistry Vol. 18 No. 4 2009
to predict the hydrate formation condition of natural gases as
a function of pressure and temperature respectively. Tables 1
and 2 show the tuned coefficients for Equations (3) to (6).
In brief, the following steps are repeated to tune the cor-
relations coefficients.
(1) Correlate the hydrate formationcondition as a function
of pressure and temperature for the selected molecular weight.
(2) Repeat step 1 for other molecular weights.
(3) Correlate corresponding polynomial coefficients,
which were obtained for different pressures versus molecu-
lar weight, a = f(M), b = f(M), c = f(M), d = f(M)
[see Equations (3)(6)].
(4) Calculate the effective hydrate formation condition as
a function of pressure and temperature fromEquations (1) and
(2), respectively.
Equations (1) and (2) represent the new developed corre-
lation in which four coefficients are used to correlate hydrate
formation pressure and temperature of natural gases.
ln(T) =a+b

1
P

+c

1
P

2
+d

1
P

3
(1)
ln(P) =a+b

1
T

+c

1
T

2
+d

1
T

3
(2)
Where:
a =A
1
+B
1
M +C
1
M
2
+D
1
M
3
(3)
b =A
2
+B
2
M +C
2
M
2
+D
2
M
3
(4)
c =A
3
+B
3
M +C
3
M
2
+D
3
M
3
(5)
d =A
4
+B
4
M +C
4
M
2
+D
4
M
3
(6)
The coefficients shown in Equations (1) and (2) are corre-
lated as a function of molecular weight (M) in Equations (3)
to (6). The optimum derived coefficients used in Equations
(3) to (6) are given in Tables 1 and 2. These optimum tuned
coefficients help to cover data from Katz (1945) gravity chart
in temperature variation of 260 K to 298 K as well as the gas
molecular weights within the range of 16 to 29.
Table 1. Tuned coefficients usedin Equations (2) to (5) to predict hydrate
formation pressure in kPa (given temperature in K) by Equation (2)
Natural gas with Natural gas with
Coefficient molecular weight less than 23 molecular weight more than 23
265 K <Temperature <298 K 265 K <Temperature <298 K
A
1
2.8375555003183 10
5
9.648514828101110
4
B
1
4.18872372153310
4
1.298725522356210
4
C
1
2.042678568016110
3
5.694312318349310
2
D
1
3.299942786000710
1
8.0291736544591
A
2
2.351857711359810
8
8.385194230576710
7
B
2
3.47031107097910
7
1.129244354540310
7
C
2
1.692130767475810
6
4.948120321049710
5
D
2
2.733152657104410
4
6.974372941963910
3
A
3
6.489903550602810
10
2.428395048723210
10
B
3
9.572892150525610
9
3.271332587617810
9
C
3
4.66723344370710
8
1.432596989639410
8
D
3
7.537325707238710
6
2.01853614754410
6
A
4
5.965347741555210
12
2.343053806137910
12
B
4
8.79637286487510
11
3.157018117578810
11
C
4
4.288197224870110
10
1.3818050947490810
10
D
4
6.924141404623510
8
1.946350673339810
8
Table 2. Tuned coefficients used in Equations (2) to (5) to predict hydrate formation temperature in K (given pressure in kPa) by Equation (1)
Natural gas with Natural gas with Natural gas with
Coefficient molecular weight more than 23 and pressure molecular weight less than 23 and molecular weight less than 23 and
1200 kPa<P< 40000 kPa pressure 1200 kPa<P<5000 kPa pressure range 5000 kPa<P<40000 kPa
A
1
6.4185071105353 4.1812132784232 7.0959703947586
B
1
8.801710787566610
2
1.472639349108 2.180603007079510
1
C
1
3.557342935713710
3
7.274538627125110
2
1.130593343979410
2
D
1
4.749984388124410
5
1.189779587988410
3
1.92720319562610
4
A
2
8.642628913986810
3
4.528497500018110
4
1.258464942159210
5
B
2
1.024330785229710
3
6.862812444981310
3
1.899311176633610
4
C
2
4.0966392546550910
1
3.424072186040610
2
9.526005812723410
2
D
2
5.445005075772910
1
5.642533019 1.580682008902910
1
A
3
1.15964303046210
7
8.31707507322510
7
9.219038228315110
8
B
3
1.385902777410910
6
1.260481024922510
7
1.403041056748810
8
C
3
5.535314827082210
4
6.301857946613810
5
7.082041798999410
6
D
3
7.33999454764510
2
1.040884843097310
4
1.181876347194910
5
A
4
4.020095147537710
9
5.858977399338610
9
2.105354862621110
12
B
4
4.79133183306210
8
9.6634962535354 10
8
3.21399259721910
11
C
4
1.903632529600910
7
5.1347314224130710
7
1.627476726273910
10
D
4
2.511329740415610
5
8.8781858649210
5
2.72488432457310
8
3. Results
The error analysis for the correlation involves check-
ing the accuracy of the model against the extracted values
from the Katz (1945) gas-gravity chart. The error anal-
ysis includes analysis for the following pressure ranges;
below 5 MPa, 510 MPa, 1015 MPa, 1520 MPa,
2025 MPa, 2530 MPa, and above 30 MPa, as well as an
overall analysis for each given gas specific gravity (Table 3).
Journal of Natural Gas Chemistry Vol. 18 No. 4 2009 3
Table 3. Summary of new methods results for the prediction of hydrate formation condition in
comparison with the data from Katz (1945) gravity chart
Gas specific Pressure Average Gas specific Pressure Average
gravity range (MPa) absolute error (%) gravity range (MPa) absolute error (%)
0.552 Below 5 0.13 0.8 Below 5 0.13
510 0.04 510 0.02
1015 0.03 1015 0.01
1520 0.02 1520 0.01
2025 0.04 2025 0.01
2530 0.01 2530 0.02
Above 30 0.20 Above 30
Overall 0.09 Overall 0.06
0.6 Below 5 0.09 0.9 Below 5 0.21
510 0.05 510 0.30
1015 0.04 1015 0.13
1520 0.04 1520 0.13
2025 0.03 2025 0.37
2530 0.02 2530 0.50
Above 30 0.12 Above 30
Overall 0.06 Overall 0.23
0.7 Below 5 0.10 1 Below 5 0.22
510 0.01 510 0.30
1015 0.01 1015 0.08
1520 0.01 1520 0.28
2025 0.01 2025 0.48
2530 0.01 2530
Above 30 0.04 Above 30
Overall 0.05 Overall 0.24

Average absolute deviation percent: 0.12%

3.1. Comparison with existing correlations
Several reputable correlations were chosen as a basis of
comparison; Hammerschmidt (1934) [9], Berg (1986) [10],
Kobayashi et al. (1987) [11], and Motiee (1991) [12]. Us-
ing the same values (temperature, pressure, gas gravity), the
results of new proposed correlations were compared to the ex-
isting correlations with encouraging results. Tables 4 and 5
present the comparison of results for the proposed method and
existing correlations. Table 5 shows the proposed correlation
has better performance than other existing correlation to esti-
mate hydrate formation conditions.
Table 4. New correlation results in comparison with experimental dada and existing correlations
Temperature (K)
Pressure (kPa) Gas molecular weight Experimental temperature Kobayashi Berg Motiee Hammerschmidt New correlation
[2] (1987) (1986) (1991) (1934)
3157.8 16 274.82 275.04 275.04 278.04 283.71 275.21
4136.85 16 277.59 277.71 277.65 280.26 285.98 277.33
5515.81 16 280.37 280.48 280.37 282.59 288.59 279.59
1723.69 17.4 277.59 277.21 272.43 275.43 279.21 277.56
3309.48 17.4 283.15 282.82 283.98 280.98 284.09 282.91
6756.86 17.4 288.71 288.37 291.65 286.48 290.59 288.91
18098.74 17.4 294.26 291.54 296.87 293.15 301.98 295.1
2688.96 18.85 283.15 285.09 284.37 281.71 282.43 284.42
14134.25 18.85 294.26 292.21 296.82 293.54 298.82 295.72
827.37 20.3 274.82 277.32 263.37 273.93 274.71 274.83
2344.2 20.3 283.15 285.82 284.09 282.71 281.43 283.57
4757.38 20.3 288.71 290.59 291.65 287.98 287.21 288.62
23442 20.3 297.04 286.59 298.32 297.87 305.54 297.61
496.42 23.2 272.04 274.04 252.82 273.15 272.09 272.72
1930.53 23.2 283.15 285.59 282.98 284.26 279.98 283.98
11721.09 23.2 294.26 291.04 296.93 295.82 296.54 294.64
758.42 26.1 277.59 278.32 265.93 278.87 274.26 277.45
1585.79 26.1 283.15 284.21 280.93 284.32 278.65 282.57
17926.37 26.1 297.04 282.93 298.15 297.93 301.87 296.74
413.69 29 274.82 273.87 250.59 274.71 271.26 275.7
1344.48 29 283.15 281.48 278.76 283.15 277.59 282.66
3033.69 29 288.71 286.43 289.65 288.04 283.37 289.66
4 Alireza Bahadori et al./ Journal of Natural Gas Chemistry Vol. 18 No. 4 2009
Table 5. New correlation accuracy in comparison with experimental data and other existing correlations
Error, percentage
Pressure (kPa) Gas molecular weight
Experimental
Kobayashi Berg Motiee Hammerschmidt New correlation
temperature (K)
(1987) (1986) (1991) (1934)
3157.8 16 274.82 0.08 0.08 1.17 3.23 0.14
4136.85 16 277.59 0.04 0.02 0.96 3.02 0.1
5515.81 16 280.37 0.04 0 0.79 2.93 0.28
1723.69 0.6 277.59 0.14 1.86 0.78 0.58 0.01
3309.48 0.6 283.15 0.12 0.29 0.77 0.65 0.07
6756.86 0.6 288.71 0.12 1.02 0.77 0.65 0.07
18098.74 0.6 294.26 0.93 0.89 0.38 2.62 0.29
2688.96 0.65 283.15 0.69 0.43 0.51 0.26 0.45
14134.25 0.65 294.26 0.7 0.87 0.25 1.55 0.5
827.37 0.7 274.82 0.91 4.16 0.32 0.04 0
2344.2 0.7 283.15 0.94 0.33 0.16 0.61 0.15
4757.38 0.7 288.71 0.65 1.02 0.25 0.52 0.03
23442 0.7 297.04 3.52 0.43 0.28 2.86 0.19
496.42 0.8 272.04 0.74 7.07 0.41 0.02 0.25
1930.53 0.8 283.15 0.86 0.06 0.39 1.12 0.29
11721.09 0.8 294.26 1.1 0.91 0.53 0.77 0.13
758.42 0.9 277.59 0.26 4.2 0.46 1.2 0.05
1585.79 0.9 283.15 0.37 0.78 0.41 1.59 0.2
17926.37 0.9 297.04 4.75 0.37 0.3 1.63 0.1
413.69 1 274.82 0.34 8.81 0.04 1.29 0.32
1344.48 1 283.15 0.59 0.37 0.3 1.63 0.1
3033.69 1 288.71 0.79 0.33 0.23 1.85 0.33
Overall error 18.68 42.49 10.46 30.62 4.05
Average error in percentage 0.84 1.93 0.48 1.39 0.18
As can be seen from Tables 4 and 5, new proposed corre-
lations show consistently accurate results across all pressure
ranges and specific gas gravities when predicting the hydrate
forming temperature for a specified pressure. For all con-
ditions, new correlation showed deviation in average 0.18%.
This consistency could not be matched by any of the existing
correlations within the investigated range.
Figures 1 to 5 illustrate the performance of newdeveloped
correlations against the data from Katzs Chart. These graphs
show the excellent performance of proposed correlation for
both hydrate formation pressure and temperature. These cor-
relations cover molecular weight between 16 to 29 and tem-
peratures between 265 to 298 K as well as pressures between
1200 to 40000 kPa.
Figure 1. Comparison of obtained results of the new developed method for
predicting hydrate formation pressure with data derived from Katz (1945)
gravity chart for natural gases with molecular weight less than 23
Figure 2. Comparison of obtained results of new developed method for pre-
dicting hydrate formation pressure with data derived from Katz (1945) gravity
chart for natural gases with molecular weight more than 23
Figure 3. Comparison of obtained results of the new developed method for
predicting hydrate formation temperature with data derived from Katz (1945)
gravity chart for natural gases with molecular weight less than 23 and pressure
less than 5000 kPa
Journal of Natural Gas Chemistry Vol. 18 No. 4 2009 5
Figure 4. Comparison of obtained results of the new developed method for
predicting hydrate formation temperature with data derived from Katz (1945)
gravity chart for natural gases with molecular weight less than 23 and pressure
more than 5000 kPa
Figure 5. Comparison of obtained results of the new developed method for
predicting hydrate formation temperature with data derived from Katz (1945)
gravity chart for natural gases with molecular weight more than 23
4. Conclusions
Novel correlation was developed for accurate prediction
of hydrate forming conditions of natural gases based on the
extracted data from Katz gas-gravity chart. The new proposed
correlation provided reliable results in comparison with other
existing correlations for pressures between 1200 to 40000 kPa
and temperatures between 265 K and 298 K, as well as the
gas molecular weight within the range 16 to 29. New pro-
posed correlation shows consistently accurate results across
all pressure ranges and gas molecular weights. This consis-
tency could not be matched by any of the widely accepted ex-
isting correlations within the investigated range. For all con-
ditions, new correlation showed absolute deviation in average
0.18%.
Acknowledgements
The lead author acknowledges the Australian Department of Ed-
ucation, Science and Training for Endeavour International Postgrad-
uate Research Scholarship (EIPRS), the Office of Research & De-
velopment at Curtin University of Technology, Perth, Western Aus-
tralia for providing Curtin University Postgraduate Research Schol-
arship and the State Government of Western Australia for providing
top up scholarship through Western Australian Energy Research Al-
liance (WA: ERA). Useful comments fromtwo anonymous reviewers
and the editor that improved the original version of the paper are ac-
knowledged. The authors also acknowledge Ashley Hunt and Liam
McCullum for their assistance.
Nomenclature
ACoefficient
BCoefficient
C Coefficient
DCoefficient
P Pressure, kPa
T Temperature, K
MMolecular weight
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