62-01-02

A Rapid Appro~ilD.ate Meth.od For Th.e

EstilD.ation of Hydrocarhon Dew Points of Clean
Pipeline Natural Gases
By K. AZIZ* and G. W.

GOVIER~'*

(13th Annual Technical Meeting, Calgary, May, 1962)

ABSTRACT

INTRODUCTION

CALCULATION OF HYDROCARBON

A "theoretical" correlation of the

effect of pressure on the hydrocarbon dew point temperature of clean
pipeline gases is presented. The
correlation was developed from calculated dew point data on thirteen
gas analyses from ten gas fields in
Alberta. The dew points were calculated by conventional trial and
error method and NGAA equilib
rium ratio charts. The data are
correlated by means of a wetness
parameter based on the amounts of
propane and heavier components in
the gas and equilibrium ratios for
those components at arbitrarily
selected conditions.

IPELINE natural gases, which

are composed mainly of a mixture of paraffin hydrocarbon gases,
nitrogen, carbon dioxide and water
vapor, normally exhibit two kinds
of dew points. These are hydrocarbon dew points and water dew
points.

'DEW POINTS FROM GAS

The correlation allows the quick

estimation of the hydrocarbon dew
points of clean pipeline gases with.
out the usual trial and error procedure. For more accurate results
the dew points calculated from this
correlation may be used as the first
estimate in the conventional trial
and error calculations. The calculated dew points are usually within
4F of the results from conventional calculations over the normal
range of pipeline operating pres
sure and, for pipeline natural gases
free of contaminants, such as glycol
or compressor oil, are within about
the same limits when compared
with measured dew points.
The correlation does not apply to
the prediction of dew point temperatures for pipeline gases containing even small quantities of alcohol,
glycol or compressor oil.

* Assistant

Professor of Petroleum
Engineering, University of Alberta, Edmonton.

** Professor

of Chemical Engineering, Dean of Faculty of Engineering, University of Alberta,

Edmonton.

Technology, Spring, 1962, Calgary

The dew point is the temperature,

at a certain pressure, at which the
first drop of liquid is formed or is
just about to form. In the case of
water dew points, the liquid formed
is water and in the case of hydrocarbon dew points the liquid formed
is a mixture of the hydrocarbons
contained in the gas. If a pipeline
gas, as a result of processing, con
tains contaminants such as glycol,
a third type of dew points may also
be observed. The liquid formed in
this case will be a mixture of hydrocarbons and the contaminant. Because of the higher boiling point of
the contaminant, the presence of
this component in the gas would
raise the dew point temperature.
Small amounts of nitrogen, carbon
dioxide and other non-hydrocarbon
constituents may also be present in
the dew formed, depending upon
the concentration of these components.
In the case of clean natural gases
(free of contaminants) the hydrocarbon dew point may be determined either by direct measurement
or by calculation from the known
gas analysis. The dew points of
contaminated gases may only be
determined by actual measurement.
(If the amount and nature of the
contaminants
were
accurately
k now n theoretical calculations
should be possible.)

ANALYSIS

The dew point is the condition at

which the first droplet of liquid (or
dew) is formed, and is computed
as the temperature, T, and pressure,
P, at which the sum of the
terms equals unity.
2:

k = 2:

= 1.0 at dew point.

~
(1)

where:
y: mole fraction of the hydrocarbon in the gas phase on a
water free basis.
x: mole fraction of the hydrocarbon in the droplet of liquid
formed on a water free basis.
K: equilibrium ratio for the hydrocarbon at pressure P and
at temperature T.
The procedure for calculation of the
dew point temperature knowing the
pressure and the composition of the
gas is as follows:
(1)

Assume a dew point temperature.

(2)

Determine the K values for

each component at the pressure of interest and assumed
temperature (K values may
be obtained from the NGAA
correIation).

(3) Calculate the composition in

the liquid phase (x) for each
component (assuming that
the original composition of
the gas is the same as the
composition of the gas after
the first droplet of liquid is
formed).
9

(4) Check the sum of all the mole

fractions in the liquid phase
(x). This sum must be equal
to 1.00 if the temperature assumed is correct_
(5) If the sum of the liquid mole
fractions is not equal to
1.00, repeat calculations (2)
through (4), assuming a different dew point temperature.
In order to perform the above
calculations, an analysis of the gas
and the K-value for each component in the gas as a function of
pressure and temperature must be
available. These are now discussed
separately.

to composition would be most accurate.

Several correlations are available
for the determination of K values.
All of these correlations are based
on the assumption that the components of a natural gas behave similarly with respect to their physical
properties. This behavior of hydrocarbons as a family has been verified. The presence of non-hydrocarbons such as carbon dioxide,
nitrogen and hydrogen sulphide reduces the accuracy of these correlations as these gases do not belong
to the hydrocarbon family.
The Kellogg fugacity charts (1)
and the NGAA charts (2) have

found wide use for predicting equilibrium constants for natural gas
systems. The NGAA charts which
are contained in the Natural Gasoline Supply Men's Association Data
Book, were used for calculations in

(1) Benedict, M., et al., "Vapor

Liquid Equilibrium in Mixtures
of Light Hydrocarbons," M. W.
Kellogg Company. New York;
Chem. Eng. Progr., 46 (3): 20
(1950).
(2) Natural Gasoline Supply Men's
Association, Engineering Data
Book (1957).

ANALYSIS OF GAS

The dew points of pipeline gases

depend to a large extent on the
propane and heavier hydrocarbons.
The propane-plus content of most
pipeline gases is quite small and
the methods of analysis ordinarily
used are least accurate for these
components. This is illustrated by
Table I which reports the results
of the analysis of the same gas by
eight different laboratories. The
analyses appear reasonably consistent but the variation in the relative
amounts of propane and higher
hydrocarbons is sufficient to cause
a considerable difference in calculated dew point temperature. This
will be discussed further.
Addition of air to the gas sample
or the condensation of heavy hydrocarbons from a gas will result in
inaccurate analysis. The gas may
be contaminated by air if the
sample container is not properly
purged. The condensation of heavy
hydrocarbons may occur if the gas
is cooled below its dew point during
the expansion of the gas from a
high pressure pipeline to a low pressure container or from a high pressure bomb to a low pressure gas
intake of an analysis system.
Hydrocarbon gas analyses are
usually obtained by chromatographic methods. Special care should
be taken to ensure proper sampling
of the gas.

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EQUILIBRIUM RATIO, K

Ideally K values should be determined experimentally for the system under consideration. This is
seldom practical and for most calculations the engineer must resort
to generalized empirical correlations. Correlations based on data
from systems similar with respect
10

Journal of Canadian Petroleum

this investigation. These charts are

based on the assumption that the
K value for a component in a gas
is a function of the pressure, temperature and the convergence pressure only.
The convergence pressure is employed as an approximate measure
of the composition of the gas. The
calculation procedures for the convergence pressure are described in
the NGSMA Data Book and the
"Handbook of Natural Gas Engineering" by Katz and Associates (31.

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The accuracy of dew point calculations depends on all of the factors discussed above. With a precision analysis and suitably chosen
K values calculated dew points for
uncontaminated gases may be expected to check measured values
within about 5F. Normal commercial gas analyses may lead to
much greater discrepancies and if
inappropriate K values are used
differences between calculated and
measured dew points may easily
reach 40 or 50F.

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CALCULATED RESULTS

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The analyses and properties of 10

different Alberta gases are presented in Table II, duplicate analyses
being given for several. Dew points
were calculated from these analyses
and NGAA K data at a convergence pressure of 5000 psi. The results at pressures from 100 to 800
psia appear in Table III. The variation in calculated dew point
temperature for the duplicate analyses ranges from 2F to 25F.

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CORRELATION
The "theoretical" correlation is
based on the following considerations. (i) The dew point temperature of a gas is a function of the
pressure and gas composition. (il)
The equilibrium constants are a
function of the pressure, temperature and composition.
Oii) For
natural gas systems the propaneplus content of the natural gas
might be expected to have the dominant effect on the hydrocarbon dew
point. Ov) If the value of K is
selected for each component at
some arbitrary average pressure
and temperature, the dew point
temperature might be considered to

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(3) Katz, D. L., et al., "Handbook
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McGraw-Hill, 1959.

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Technology, Spring, 1962, Calgary

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be a function of the pressure and

a wetness parameter, W, defined by
Equation (2).

K
at arbit
rary constant
P and T 2)

where C n is the heaviest hydrocarbon present in the gas.

For the calculations of the wetness parameter, W, values of K at
oaF and 500 psia were selected.
These values of K are called variable A and are tabulated in Table
IV for reference. Equation (2)
may now be written as:

Cn

~~

1
A

(3)

C3

The values of Wand dew point

temperatures at 100, 300,500, 600
and 800 psia, were calculated for
gas samples 24, 242, 20, '23, 1, 15, 18,
31, 33. 332, 36, 22 and 362. The calculated data are tabulated in Table
III.
The dew point temperatures are
shown for various constant pressures as a function of the wetness
parameter, W, in Figure I. Straight
line relationships were observed on
semi-logarithmic co-ordinates for
each pressure. The data are well

represented by the straight lines

except at 100 psia where a scattering up to about lOaF is observed.
The final "theoretical" correlation which is a smoothed cross plot
of Figure I is presented in Figure
II. This permits the direct estimation of the dew point temperature
at any pressure from a calculation
of the wetness parameter. If a
more accurate calculation of the
dew point is required, the calculated
dew point from the correlation may
be used as a first estimate of the
dew point in conventional calculations. The correlation eliminates
the normal time-consuming trial.
and-error calculations.
By way of example, the dew
point at 568 psia of the gas reported in Table I was calculated assuming the analysis from Laboratory
B. Conventional calculations gave
a dew point of +13F. The wetness parameter for the gas was
determined as 0.9'5 and the dew
point indicated by Figure II is
+ 16F. Other comparisons show
a check between conventional calculations and that from Figure II
of -+- 4 a F in the pressure range of
300 to 800 psia.
(This accuracy
refers to the agreement obtained
from the correlation as compared
with the conventional calculations,
not the agreement between calculated and actual dew points.)

CONCLUSION

A correlation based on theoretical

considerations has been developed
for the rapid estimation of the
hydrocarbon dew point temperature
of clean pipeline natural gases. The
correlation results in dew points
which check those determined by
conventional calculations to within
about 4F. The correlation, like
conventional calculations, does not
apply to gases contaminated with
hydrate depressants or compressor
oil.

Nomenclature

A: Equilibrium ration, K, at OaF

and 500 psia for a hydrocarbon
mixture of 5000 psi convergence
pressure.
Ct, C2 .. - C6: methane, ethane - - hexane.
K: Equilibrium ration for the hydrocarbon at pressure P and
temperature T.
P: pressure, psia.
T: dew point temperature, OF.
W: wetness parameter defined by
Equation (2).
x: mole fraction in the liquid
phase.
y: mole fraction in the vapor
phase.

ACKNOWLEDGMENT

The research reported here was

undertaken at the request of and
under the financial support of Alberta Gas Trunk Line Company
Limited.

Gas
No.
241
242
20
23
1
15
181
3b
331
332
361
22
362

TABLE III.
CALCULATED HYDROCARBON DEW POINT TEMPERATURES, OF.
Wetness
Parameter
Pressure, Psia
W
100
300
600
500
0.231
-7O
-49
-42
-38.5
0.427
-24.5
-45
-18
-16
0.353
-63
-37
-27
-2.4
0.317
-63
-40
-29
-31
0.302
-66
-43
-34
-32
0.238
-72
-44.5
-40.5
-38
-45
-18
- 6
0.582
8
0.804
-35
- 4
8
13
-11
0693
-43
1
5
0.623
-48
-15.5
2
2
0.484
-24
-53
-12
8
-14
-42
0
0.634
3
- 8.5
0.698
34
5
2
Convergence Pressure
5000 psi.
NGAA K values used;
K for C n used for C n +

12

800
-36
-15
-21.5
-26
-29
-35
- 3.5
17

10
8
3.5
4
8.5

The authors wish to acknowledge

the enthusiastic co-operation of Mr.
E. V. Hunt, Mr. C. T. McCall and
Mr. J. Bulley, all of the Alberta Gas
Trunk Line Company.

TABLE IV.
Hydrocarbon

Propane
i-Butane

_
_
_
i-Pentane ----------------n-Pentane
_
Hexane
.__
Heptane
_

r~Butane

A
0.135
0.050
0.034
0,013
0.0096
0.00335
0.009

Note: A is the equilibrium constant

K, at oaF, 500 psia and a
convergence pressure of 5000
psi.
Journal of Canadian Petroleum

9
7

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LEGEND
CALCULATED DATA
PRESSURE
SYMBOL
(psio)

100
300
500
600
800

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-70 -60 -50 -40 -30 -20

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DEW POINT TEMPERATURE. OF

Figure I.

WETNESS

600
500

~(

800
700

0.40 0.50

PARAMETER, W

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DEW POINT TEMPERATURE

60

70

80

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Figure II.
Technology, Spring, 1962, Calgary

13