0.6 sp. gr. gas (composition is shown in Fig.

20-22) has a hydrate formation temperature which is 12-13F higher than

pure methane.

FIG. 20-14
Calculated Water Content of Acid Gas Mixtures
to 10,000 psia

The presence of H2S in natural gas mixtures results in a

substantially warmer hydrate formation temperature at a
given pressure. CO2, in general, has a much smaller impact
and often reduces the hydrate formation temperature at fixed
pressure for a hydrocarbon gas mixture.
The conditions which affect hydrate formation are:
Primary Considerations
Gas or liquid must be at or below its water dew point or
saturation condition (NOTE: liquid water does not have
to be present for hydrates to form)
Temperature
Pressure
Composition
Secondary Considerations
Mixing
Kinetics
Physical site for crystal formation and agglomeration
such as a pipe elbow, orifice, thermowell, or line scale
Salinity
In general, hydrate formation will occur as pressure increases and/or temperature decreases to the formation condition.

Prediction of Sweet Natural Gas Hydrate

Conditions
Fig. 20-18, based on experimental data, presents the hydrate
pressure-temperature equilibrium curves for pure methane,
ethane, propane, and for a nominal 70% ethane 30% propane
mix.
Fig. 20-19 through 20-21, based on gas gravity, may be used
for first approximations of hydrate formation conditions and
for estimating permissible expansion of sweet natural gases
without the formation of hydrates.
bic called Structure I. Larger molecules (C3H8, i-C4H10, nC4H10) form a diamond-lattice called Structure II.
Normal paraffin molecules larger than n-C4H10 do not form
Structure I and II hydrates as they are too large to stabilize
the lattice. However, some isoparaffins and cycloalkanes
larger than pentane are known to form Structure H hydrates.13

The conditions at which hydrates can form are strongly affected by gas composition. Compositions used for the construction of Fig. 20-19 through Fig. 20-21 are given in Fig. 20-22.
The gases are saturated with water.
Example 20-3 Find the pressure at which hydrate forms for
a gas with the following composition. T = 50F.

From a practical viewpoint, the structure type does not affect the appearance, properties, or problems caused by the hydrate. It does, however, have a significant effect on the
pressure and temperature at which hydrates form. Structure
II hydrates are more stable than Structure I. This is why gases
containing C3H8 and i-C4H10 will form hydrates at higher temperatures than similar gas mixtures which do not contain
these components. The effect of C3H8 and i-C4H10 on hydrate
formation conditions can be seen in Fig. 20-19. At 1000 psia, a

Mole
Fraction
0.784
0.060
0.036
0.005
0.019
0.094
0.002
1.000

Component

Gas composition determines structure type. Mixed gases

will typically form Structure II. Limiting hydrate numbers (ratio of water molecules to molecules of included gaseous component) are calculated using the size of the gas molecules and
the size of the cavities in H2O lattice.

C1
C2
C3
iC4
nC4
N2
CO2
Total

Mole Wt
16.043
30.070
44.097
58.124
58.124
28.013
44.010

lb per lb-mol
of Mixture
12.58
1.80
1.59
0.29
1.10
2.63
0.09
20.08

Mole wt. of gas mixture = 20.08

20-10

MWgas
MWair

20.08
= 0.693
28.964

FIG. 20-15
Calculated Water Content of Acid Gas Mixtures

Example 20-5 How far may a 0.6 gravity gas at 2,000 psia and
100F be expanded without hydrate formation?

From Fig. 20-19 at 50F

P = 320 psia for 0.7 gravity gas
Example 20-4 The gas in Example 20-3 is to be expanded from
1,500 psia to 500 psia. What is the minimum initial temperature
that will permit the expansion without hydrate formation?
The 1,500 psia initial pressure line and the 500 psia final pressure line intersect just above the 110F curve on Fig. 20-21. Approximately 112F is the minimum initial temperature.

On Fig. 20-20 find the intersection of 2,000 initial pressure line

with the 100F initial temperature curve. Read on the x-axis the
permissible final pressure of 1100 psia.
Example 20-6 How far may a 0.6 gravity gas at 2,000 psia and
140F be expanded without hydrate formation?
On Fig. 20-20, the 140F initial temperature curve does not intersect the 2,000 psia initial pressure line. Therefore, the gas may

20-11

FIG. 20-16
Comparison of Experimental vs. Calculated Water Contents for Acid Gases

Mixture

Water Content lb/MMscf

Fig. 20-12
Eq 20-1
& 20-13

T, F

P, psia

11% CO2/89% C1
11% CO2/89% C1

100
160

2000
1000

40.6
286

42
277

39.2
287

43
285

20% CO2/80% C1
20% CO2/80% C1
20% CO2/80% C1

100
160
160

2000
1000
2000

40.6
282
172

43
278
182

44.1
287
172

46
290
194

8% H2S/92% C1

130

1500

111

105

112

106

27.5% H2S/72.5% C1

160

1367

247

258

273

260

17% H2S/83% C1

160

1000

292

278

290

293

C1/CO2/H2S
30%/60%/10%

100

1100

81

72

NA

86

C1/CO2/H2S
9%/10%/81%

100

1900

442

72

NA

NA

5.31% C1/94.69% CO2

5.31% C1/94.69% CO2

77
122

1500
2000

109.2
164.6

38
105

NA
NA

NA
NA

Experimental

FIG. 20-17
Water Content of 5.31% C3/94.69% C1 Gas in Equilibrium with Hydrate

20-12

Fig. 20-15

be expanded to atmospheric pressure without hydrate formation.

Nitrogen is assumed to be a non-hydrate former and is also

assigned a K-value of infinity.

Conditions predicted by Fig. 20-19 through 20-21 may be significantly in error for compositions other than those used to derive
the charts. For more accurate determination of hydrate formation
conditions, the following procedures should be followed. In addition, Fig. 20-20 and 20-21 do not account for liquid water and liquid
hydrocarbons present or formed during the expansion. These can
have a significant effect on the outlet temperature from the pressure reduction device.

The Kvs values are used in a dewpoint equation to determine the hydrate temperature or pressure. The calculation is
iterative and convergence is achieved when the following objective function (Eq 20-4) is satisfied.

Hydrate Prediction Based on Composition

for Sweet Gases
Several correlations have proven useful for predicting hydrate formation of sweet gases and gases containing minimal
amounts of CO2 and/or H2S. The most reliable ones require a
gas analysis. The Katz method14,15 utilizes vapor solid equilibrium constants defined by the Eq 20-3.
y
Kvs =
Eq 20-3
xs
WARNING: Not good for pure components only mixtures.
The applicable K-value correlations for the hydrate forming
molecules (methane, ethane, propane, isobutane16, normal butane17, carbon dioxide, and hydrogen sulfide) are shown in Fig.
20-23 to 20-29. Normal butane cannot form a hydrate by itself
but can contribute to hydrate formation in a mixture.
For calculation purposes, all molecules too large to form hydrates have a K-value of infinity. These include all normal paraffin hydrocarbon molecules larger than normal butane.

i=n

(yi / Kvs )

= 1.0

Eq 20-4

i=1

Prudence should be exercised when some higher molecular

weight isoparaffins and certain cycloalkanes are present as
they can form Structure H hydrates.
Example 20-7 Calculate the pressure for hydrate
formation at 50F for a gas with the following composition.
Mole
Fraction
in Gas
0.784

Kvs

y/Kvs

Kvs

y/Kvs

2.04

0.384

1.75

0.448

Ethane

0.060

0.79

0.076

0.50

0.120

Propane

0.036

0.113

0.319

0.072

0.500

Isobutane

0.005

0.046

0.109

0.027

0.185

n-Butane

0.019

0.21

0.090

0.21

0.090

Nitrogen

0.094

0.000

0.000

Carbon dioxide

0.002

3.0

0.001

1.9

Component
Methane

Total
* Infinity

at 300 psi

1.000

at 400 psi

0.979

Interpolating linearly, y/Kvs = 1.0 at 305 psia

FIG. 20-19

FIG. 20-18

Pressure-Temperature Curves for

Predicting Hydrate Formation

Conditions for Hydrate Formation for Light Gases

20-13

0.001
1.344

The experimentally observed hydrate-formation pressure at

50F was 325 psia.

data. Plot the results on Fig. 20-30. Sample calculations

for 200 and 300 psia are provided below. This calculation
has been repeated for 400, 500, 800 and 1000 psia to develop Fig. 20-30.

Example 20-8 The gas with the composition below is at

3500 psia and 150F. What will be the hydrate conditions when
this gas is expanded?

T = 40F

200 psia

300 psia

y/Kvs
0.4119

Kvs
1.75

y/Kvs
0.5295

Mole Fraction
0.9267

C1

0.9267

Kvs
2.25

0.0529

C2

0.0529

0.50

0.1058

0.205

0.2580

0.0138

C3

0.0138

0.055

0.2509

0.030

0.4600

0.0018

iC4

0.0018

0.0225

0.0800

0.0105

0.1714

nC4

0.0034

nC4

0.0034

nC5

0.0014

C5

0.0014

1.0000

Total

1.0000

Component
C1
C2
C3
iC4

Total

0.8486

1.4189

y/Kvs = 1.0 @ 227 psia

Solution Steps:

3. The intersection of the lines in Fig. 20-30 will be the point

at which hydrates start to form. In this example, the result is 500 psia and 52F.

1. Make several adiabatic flash calculations at different

pressures and plot on a pressure versus temperature
graph. (See Fig. 20-30)
Initial
Pressure,
psia
3500

Initial
Temperature,
F
150

Final
Pressure,
psia
300

Final
Temperature,
F
38

3500

150

400

45

3500

150

500

52

3500

150

600

58

3500

150

700

64

Note: Fig. 20-20 would predict permissable expansion only to

a pressure around 700 psia.
The Katz correlation is not recommended above 1000-1500
psia, depending on composition. Prediction of hydrate formation conditions at higher pressures requires the use of other
methods. Sloan, et.al.18 present an alternate set of Kvs values
which, in general, are valid to 4000 psia. McLeod & Campbell19
present experimental hydrate data for natural gas mixtures

2. Assume some temperature and predict the hydrate formation pressure for this gas using the solid-vapor K-

FIG. 20-21
Permissible Expansion of a 0.7-Gravity Natural Gas
Without Hydrate Formation

FIG. 20-20
Permissible Expansion of a 0.6-Gravity Natural Gas
Without Hydrate Formation

See Caution on Fig. 20-19.

See Caution on Fig. 20-19.

20-14

up to 10,000 psia as well as a correlation for estimating high

pressure hydrate formation conditions.Blanc & Tournier-Lasserve20 provide experimental hydrate data to 14,500 psia
and compare prediction correlations with experimental
data.

Example 20-9 Estimate the hydrate formation temperature at 610 psia of a gas with the following analysis using Fig.
20-31.
Component
N2
CO2
H2S
C1
C2
C3
iC4
nC4
C5+

Hydrate Predictions for High CO2/H2S

Content Gases
The Katz method of predicting hydrate formation temperature gives reasonable results for sweet paraffin hydrocarbon
gases. The Katz method should not be used for gases containing significant quantities of CO2 and/or H2S despite the fact
that Kvs values are available for these components. Hydrate
formation conditions for high CO2 /H2S gases can vary significantly from those composed only of hydrocarbons. The addition
of H2S to a sweet natural gas mixture will generally increase
the hydrate formation temperature at a fixed pressure.21

MW = 19.75

1. Enter left side of Fig. 20-31 at 600 psia and proceed to

the H2S concentration line (4.18 mol%)
2. Proceed down vertically to the specific gravity of the gas
( = 0.682)
3. Follow the diagonal guide line to the temperature at the
bottom of the graph (T = 63.5F).
4. Apply the C3 correction using the insert at the upper left.
Enter the left hand side at the H2S concentration and
proceed to the C3 concentration line (0.67%). Proceed
down vertically to the system pressure and read the correction on the left hand scale (2.7F)

FIG. 20-22
Gas Compositions Used for Fig. 20-19 through 20-21
Mole Fraction
0.9267
0.8605
0.0529
0.0606
0.0138
0.0339
0.0018
0.0084
0.0034
0.0136
0.0014
0.0230
0.603
0.692

0.7350
0.1340
0.0690
0.0080
0.0240
0.0300
0.796

= 0.682

Solution Steps:

A method by Baille & Wichert for predicting the temperature of high H2S content gases is shown in Fig. 20-3122. This
is based on the principle of adjusting the propane hydrate
conditions to account for the presence of H2S as illustrated
in the following example.

C1
C2
C3
iC4
nC4
nC5
Sp. Gr.

mol %
0.30
6.66
4.18
84.27
3.15
0.67
0.20
0.19
0.40

Note: The C3 temperature correction is negative when on the

left hand side of the graph and positive on the right hand side.
TH = 63.5 2.7 = 60.8F
Fig. 20-31 was developed based on calculated hydrate conditions using the Peng-Robinson EOS. It has proven quite accurate when compared to the limited amount of experimental

FIG. 20-23
Vapor-Solid Equilibrium Constants for Methane

20-15