TECHNICAL NOTE

Correlation Accurately Predicts Hydrate

Forming Pressure of Pure Components
A. BAHADORI*
National Iranian South Oil Co. (NISOC)
*currently with Curtin University of Technology, Australia

Abstract
Gas hydrates are a well-known problem in the oil and gas industry when they agglomerate and plug pipelines and process
equipment. This paper presents a new correlation that predicts
hydrate formation pressure of pure alkanes, acid gases and nitrogen as a function of molecular weight at a given temperature.
This correlation covers a temperature range between 263 and
293
K. The results show an average absolute deviation of 3.06%
from typical experimental data for light alkanes and 1.4165%
for non- hydrocarbons. The average absolute deviation for all
data used in this work is 2.24%. The new correlation can be
improved if more experimental data will be available in future.

Methodology for Correlation

Development

The required data to develop this correlation include experimental temperature and pressure(3-13) for different pure
components with different molecular weights. In previous
work(14), a numerical method was applied to analyze gas hydrate
formation in a multi- component system, and in this work,
hydrate formation pressure for pure gas components is predicted
accurately by proposing a new and simple correlation. The
following methodology has been applied to develop this
correlation.
First of all, hydrate formation pressure is correlated as a function of hydrate formation temperature for different pure alkane
components. 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
Equation
Introduction
(1) to predict the hydrate formation pressure of different pure alGas hydrates are ice-like crystalline structures that form when kane components as a function of temperature. Table 1 shows the
a mixture of water and gas molecules exist under favourable con- tuned coefficients for Equations (2) to (5).
In brief, the following steps are repeated to tune this correladitions, especially at low temperatures and high pressures. In the
hydrate formation process, gas molecules are entrapped into cavi- tions coefficients.
1. Select a component and determine the molecular weight.
ties formed by water molecules. Usually light molecules such as
2. Correlate the experimental hydrate formation pressure as a
methane, ethane, propane, isobutene, nitrogen, carbon dioxide
function of temperature for the selected component.
and hydrogen sulfide will form hydrates, however, several heavy
3. Repeat step 2 and 3 for other data and for other components.
hy- drocarbons such as benzene, cyclopentane, isopentane, 4. Correlate corresponding polynomial coefficients which were
methylcy- clohexane and 2,3-dimethylbutane have been recently obtained for different molecular weights vs. gas mo- lecular
identified as hydrate formers(1).
weight, a = f(M), b = f(M), c = f(M), d = f(M) [see Equations (2)
Gas hydrates are a serious problem in the oil and gas industry (5)].
because they plug production and gas transmission pipelines and
TAble 1: Tuned coefficients used in equations (2) to (5)
damage process equipment. It is possible to keep the operating
for light alkanes (CH4, C2H6, C3H8 and Iso-C4H10).
conditions at a level where hydrate formation cannot occur by applying heat, insulating the pipelines and using chemical additives
Symbol
Coefficient
as inhibitors. To prevent the problems caused by hydrates, it is
A1
-68018798
im- portant to predict the hydrate formation temperature and
4585116.8
B1
pressure accurately.
-109476.772
C1
847.49138
D1
Hammerschmidt(2) first discovered that the formation of clath763105.18
A2
rate hydrates could block natural gas transport pipelines. After
-51445.299
B2
this discovery, the oil and gas industry has been more interested
1228.4009
C2
in in- vestigating the problem.
-9.5102613
D2
This paper presents a new correlation that can predict the gas
-2854.468
A3
192.45409
hydrate formation pressure of pure alkanes, acid gases and niB3
-4.5955325
C3
trogen as a function of molecular weight and temperature. The de0.035581155
D
3
veloped correlation is applicable to a range of temperatures from
3.5603967
A4
263 K to 293 K. The results show an average absolute deviation
-0.24007044
B4
of 2.24% from typical experimental data.
0.0057325537
C
4

February 2008, Volume 47, No. 2

D4

-0.000044386756

THIS PAPER IS BEING PUBLISHED AS A TECHNICAL NOTE AND HAS NOT BEEN PEER REVIEWED.

5. Calculate the hydrate formation pressure as a function of

temperature of the hydrate formation from Equation (1).
Equation (1) presents a new correlation that calculates the hydrate-formation pressure at a given temperature.

aABMCM DM
1

................................................................ (2)

b A B M C M 2 D M 3

2
3
P a bT cT dT ........................................................................... (1)

.............................................................. (3)

where P is the hydrate-formation pressure in kPa, T is the hydrateformation temperature in K and a, b, c and d are the coefficients for
this equation. These coefficients are calculated as a function of molecular weight (M) in Equations (2) to (5). The tuned coefficients,
A1 to A4, B1 to B4, C1 to C4 and D1 to D4 are given in Table 1.

............................................................... (4)

c A3 B3 M C3 M D3 M

d A B M C M 2 D M 3
4

............................................................. (5)

TAble 2: Tuned coefficients used in equation (6) for H2S, CO2 and N2.
Coefficient

H2S

CO2

N2

A
B
C
D

54.83410342654249
0.17072345894568
-0.00000788331643
0.00000000069834

646.022299608879
4.173803856083
-0.002084943991
0.000000932307

-9199.67095444883
43.47361827674
-0.01236519841
0.00000183174

TAble 3: Comparing
calculated hydrate formation pressure for light alkanes (CH 4, C2H6, C3H8 and Iso-C4H10) with
experimental data(3-11).

Component

Temperature
(K)

Calculated
Pressure (kPa)

experimental
Pressure (kPa)

Absolute
Deviation (%)

CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
CH4
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C2H6
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
C3H8
I-C4H10
I-C4H10
I-C4H10
I-C4H10
I-C4H10
I-C4H10
I-C4H10

262.4
264.2
266.5
273.2
277.6
280.4
280.9
283.2
287.3
288.7
288.9
289.0
290.2
290.7
260.8
273.4
275.4
277.6
279.1
281.1
282.8
284.4
285.8
287.0
288.2
264.2
273.5
273.9
274.3
274.8
275.4
275.9
276.4
276.8
277.1
277.8
278.9
273.5
273.6
273.9
274.0
274.2
274.3
274.6

1,714
1,931.1
2,125.3
2,811.3
4,017.1
5,378
5,682
7,357.6
11,649
13,558
13,851
14,000
15,884
16,728
293.45
554.9
661.4
849.2
1,029.6
1,348.8
1,701.2
2,110
2,535.2
2,954.1
3,427
110.09
175.608
189.05
204.38
226.4
257.3
287.06
320.72
350.62
374.85
437.74
555.81
114.42
116.71
124.13
126.8
132.4
135.3
144.8

1,790
1,900
2,080
2,650
4,170
5,580
5,847
7,100
11,650
13,110
14,050
13,960
15,900
16,960
294
545
669
876
1,048
1,317
1,641
2,137
2,537
3,054
3,360
115
176
190
207
232
270
301
331
365
386
455
552
122
123
132
135
140
143
151

4.4341
1.6316
2.1315
5.7376
3.8088
3.756
2.9039
3.5011
0.0086
3.3043
1.4367
0.2857
0.1007
1.3869
0.1874
1.7841
1.1491
3.1559
1.7871
2.3577
3.5387
1.2796
0.071
3.3817
1.9551
4.46
0.2232
0.5025
1.2819
2.4735
4.936
4.6312
3.2053
4.1013
2.9745
3.943
0.6855
6.624
5.3894
6.3401
6.467
5.7402
5.6911
4.2818
Journal of Canadian Petroleum Technology

I-C4H10
274.8
I-C4H10
275.0
Average Absolute Deviation Percent

160
168

151.6
158.1

5.5409
6.2619
3.0615

TAble 4: Comparing
calculated hydrate formation pressure for non-hydrocarbons (N 2, CO2 and H2S) with
experimental data(12,13).
Component

Temperature
(K)

Calculated
Pressure (kPa)

N2
272.0
N2
272.6
N2
272.8
N2
273.0
N2
273.2
N2
273.4
N2
274.8
N2
275.2
N2
275.6
N2
275.8
N2
276.2
N2
276.6
N2
277.2
N2
278.2
N2
278.6
N2
279.2
N2
280.2
N2
281.2
N2
281.6
N2
282.2
N2
283.2
N2
284.2
N2
284.6
N2
285.2
CO2
273.7
CO2
274.3
CO2
275.4
CO2
276.5
CO2
277.6
CO2
278.7
CO2
279.8
CO2
280.9
CO2
281.5
CO2
281.9
CO2
282.6
CO2
282.9
H2S
272.8
H2S
277.6
H2S
283.2
H2S
285.2
H2S
288.7
H2S
291.8
H2S
295.7
Average Absolute Deviation Percent
2
3
PNHC A BP CP DP

100 NOP
AADP NOP
i

14,904
15,561
15,802
16,057
16,323
16,602
18,920
19,706
20,547
20,990
21,915
22,895
24,466
27,340
28,573
30,504
33,920
37,560
39,079
41,430
45,597
50,238
52,298
55,701
1,342.6
1,419.9
1,598
1,823
2,097
2,418
2,791
3,228
3,506
3,712
4,126
4,330
105.9
147
273
343
504.5
695
1,027

................................................................... (6)

Calculated value 1
Experimental
value

................................... (7)

PNHC is the gas hydrate formation pressure for non-hydrocarbon

components. First, the gas hydrate formation is calculated from
Equation (1) and then it is corrected using Equation (6). Tuned coefficients (A, B, C and D) for Equation (6) are reported in Table 2.
Equation (7) calculates the average absolute deviation percent between reported data and the new proposed correlation.

experimental
Pressure (kPa)

Absolute
Deviation (%)

14,480
15,300
15,910
16,010
16,620
17,730
19,150
19,660
20,670
21,580
22,390
23,100
24,830
27,360
28,270
29,890
33,940
37,490
38,610
41,440
45,900
50,660
52,290
55,430
1,324
1,420
1,613
1,848
2,082
2,413
2,786
3,213
3,530
3,709
4,130
4,323
93
157
280
345
499
689
1,034

2.9281
1.7058
0.6788
0.2935
1.7870
6.3620
1.2010
0.2339
0.5950
2.7340
2.1214
0.8874
1.4659
0.07309
1.0604
2.05419
0.0589
0.1867
1.200
0.02413
0.6601
0.8330
0.01529
0.4889
1.4048
0.0070
0.9299
1.3528
0.7204
0.2072
0.1794
0.4668
0.6798
0.0808
0.0968
0.1619
13.8709
6.8027
2.500
0.5797
1.0901
0.8708
0.67698
1.4165

Table 1 shows tuned coefficients for Equations (2) to (5). All the
coefficients are tuned simultaneously and can be tuned again if more
accurate data is reported in the future. Table 2 provides the
coefficients for Equation (6) to correct the non-hydrocarbon hy- drate
formation pressure. These coefficients have been reported to
the highest accuracy to provide gas hydrate formation pressure. Tables 3
and 4 illustrate the calculated and experimental hydrate
formation pressures of pure alkanes, N , CO and H S, and pro2

sulfide. The advantages of this of this proposed correlation are it is

simple-to-use, its portability and its high accuracy, since process
engineers can apply it even with a simple calculator. The results are in
very good agreement with the experimental data.

Results
This correlation covers pure hydrate formers including methane,
ethane, propane, iso-buthane, nitrogen, carbon dioxide and hy- drogen
February 2008, Volume 47, No. 2

vide the average absolute deviation percent between typical experimental data and calculated results. Figures 1 and 2 compare the
calculated hydrate formation pressures from the new correla- tion
with the experimental data. These graphs have been plotted in semilog scale to cover a wide range of hydrate formation pres- sures for
different pure gases. As can be seen, the results of the proposed
correlation are in an excellent agreement with the experi- mental
data, where the absolute average deviation from typical experimental data is 2.24%.

Conclusion
We developed a new correlation that predicts hydrate formation
pressure for pure alkanes, acid gases and nitrogen as a function of
molecular weight and temperature. The results of the proposed correlation are very accurate and suitable for use. Average absolute deviation from the typical experimental data is 3.06% and 1.4165%

Journal of Canadian Petroleum Technology

10

10

265

270

275

280

Methane (correlation)
Methane
(experimental) Ethane
(correlation)
Ethane
(experimental)
Propane (correlation)
Propane (experimental)
Iso-butane (correlation)

285

290

295

Temperature (K)

FIGURE 1: Comparison of experimental and calculated hydrateformation pressures for methane, ethane, propane and iso-butane.

for light alkanes and non-hydrocarbons, respectively. The average

absolute deviation for all data used in this work is 2.24%. The
new correlation can be improved when more experimental data is
available.

Acknowledgements
The author acknowledges the Australian Department of Education, Science and Training for the Endeavour International
Postgraduate Research Scholarship (EIPRS) and the Office of Research & Development at Curtin University of Technology, Perth,
Western Australia for providing a Curtin University Postgraduate
Research Scholarship.

NOmeNClATURe
AADP
A

= average absolute deviation percent

= coefficient

= coefficient

= coefficient

= coefficient

= molecular weight

NOP
P

= number of points
= hydrate formation pressure of alkanes

PNHC
T

= hydrate formation pressures of non-hydrocarbons

= temperature, K

ReFeReNCeS
1. TOHIDI, B., DANESH, A., BURGASS, R.W. and TODD, A.C., Effect of Heavy Hydrate Formers on the Hydrate Free Zone of Real
Reservoir Fluids; paper SPE 35568 presented at the European Production Operations Conference and Exhibition, Stavanger, Norway,
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Processors As- sociation, Research Report No. 45, Tulsa, OK, 1980.

Hydrate Formation Pressure (kPa)

Hydrate Formation Pressure (kPa)

10

104

103
N2
N2
(correlation)
H2S (correlation)
(experimental)
H2S
(experimental)
CO2 (correlation)
CO2 (experimental)

10

101
270

275

280

285

290

295

Temperature (K)

FIGURE 2: Comparison of experimental and calculated hydrateformation pressures for N2, H2S and CO2.

5. DYADIN, Y.A. and ALADKO, E.Y., Decomposition of the Methane Hydrate up to

10 kbar; proceedings of the 2nd International Confer- ence on Natural Gas
Hydrates, Toulouse, France, pp. 67-70, 2-6 June 1996.
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Formation Conditions for Light Alkanes and Sweet Natural Gases; Hydrocarbon
Processing, Vol. 87, No. 1, January 2008.

7. HOLDER, G.D. and GRIGORIOU, G.C., Hydrate

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ProvenanceOriginal Petroleum Society manuscript,
Correlation Ac- curately Predicts Hydrate Forming

Pressure of Pure Components (2007-035TN), first presented at the 8th

Canadian International Petroleum Conference (the 58th Annual Technical
Meeting of the Petroleum Society), June 12-14, 2007, in Calgary, Alberta.
Abstract submitted for review No- vember 26, 2006; editorial comments
sent to the author(s) September 21, 2007; revised manuscript received
September 28, 2007; paper approved for pre-press September 28, 2007;

final approval January 8, 2008.

Authors biography
Alireza Bahadori is a Ph.D. student in the
Department of Chemical Engineering at
the Curtin University of Technology, Perth,
Western Australia. Previously, he was a
Senior Process Engineer in the Petroleum
Engineering Department of the National
Iranian South Oil Company (NISOC),
Ahwaz, Iran for eight years. He also
worked for three years as a Control
Instrument Ser- vice (CIS) Technologist
for the Aghajari Oil
and Gas Company. He holds a B.Sc. degree from the Petroleum
University of of Technology, Abadan, Iran and an M.Sc. degree
from Shiraz University, both in chemical engineering. His
research areas of interest include gas processing, gas hydrates,
thermody- namics and process simulation and optimization. He is
the author and co-author of 35 international journal papers. Mr.
Bahadori
is the recipient of the Australian Governments
Endeavour Inter- national Postgraduate Research Scholarship
(EIPRS)
for
2008.
alireza.bahadori@student.curtin.edu.au.

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