UNDERSTANDING HYDROCARBON DEW POINTS

IN NATURAL GAS MIXTURES

James N. Witte,
Southwest Research Institute

INTRODUCTION
This paper will present a discussion on the hydrocarbon
dew point of a gas, and is intended as an introduction for
operations technicians to the conditions that determine a
hydrocarbon dew point value, operating concerns generated when the hydrocarbon dew point is reached, and
approaches to the management of gas quality to control
hydrocarbon dew point in pipeline systems. The hydrocarbon dew point is one of the most important parameters
defining the quality of a natural gas mixture.

Phase envelope a term synonymous with phase

diagram.
Bubble Point - a state condition at which saturated liquids
(at a point very close to the boiling point on the phase
envelope) begin to form bubbles of infinitesimally small
amounts of vapor.
Critical Point a state condition at which the densities of
the hydrocarbon liquid and vapor are equal and the point
above which no distinct liquid and vapor phases exist.

The signs of having reached hydrocarbon dew point are

readily recognizable. Evidence of reaching the hydrocarbon dew point include a high liquid line (stain) found on an
orifice plate, liquid that is found when trying to take a gas
sample or a sound speed comparison error in an ultrasonic meter diagnostic routine. One of the distinguishing
characteristics of hydrocarbon liquid is that at atmospheric pressure and temperature the liquid will rapidly vaporize
without a trace.

Cricondenbar the maximum pressure on the two phase

boundary at which both phases can co-exist and above
which no gas phase can be formed.
Cricondentherm the highest temperature at which both
phases can co-exist and above which no liquids can be
generated.
Equations of State computational models that are
used to predict the physical characteristics of hydrocarbon mixtures in terms of density, phase, and vapor-liquid
equilibrium.

The formation of hydrocarbon liquids can pose several

operating problems. The liquids can accumulate in a low
point in the pipeline or move as a collective slug of liquid.
If they reach a compressor, a boiler, or a gas turbine the
results could be a catastrophic failure of the equipment.
Hydrocarbon liquids can also bias gas analysis equipment
and prevent gas operated pneumatic controls from functioning properly. Therefore, understanding the conditions
under which hydrocarbon liquids will form and precautions
that can be taken to avoid hydrocarbon liquid formation is
important.

PHASE DIAGRAMS
In order to understand the phase change phenomenon it
is useful to study calculated phase diagrams generated
by equations of state. Two commonly utilized equations
of state using a cubic formulation are the Peng-Robinson
and Suave-Redlich-Kwong equations. These equations
are used to compute the density of a specified hydrocarbon mixture at a given pressure and temperature. They
are particularly useful in determining the pressure and
temperature regions at which the hydrocarbon mixture, as
a vapor, will begin to condense to a liquid. This region of
condensation is referred to as the dew point region of the
phase envelope.

BACKGROUND
For this discussion we should begin with a few definitions:
Hydrocarbon Dew Point that state condition at which
the first traces of hydrocarbon liquid droplets begin to condense out of a natural gas mixture.

Figure 1 is an example Pressure Temperature (PT) phase

diagram computed using the Gulf Coast gas composition
described in AGA Report 8[1]. The phase envelope is plotted as a function of pressure and temperature.

State Condition A specific pressure and temperature.

Phase one of the three forms of matter: solid, liquid, or
vapor (gas).

Three important points along the phase envelope are the

critical point, the cricondenbar, and the cricondentherm.
The critical point is the location at maximum pressure and
temperature on the bubble point curve and at the beginning of the dew point curve. The region directly above and
to the left of the phase envelope is the liquid phase. Inside

Phase Diagram a graphical plot of the two phase (vapor

and liquid) boundary plotted as a function of pressure and
temperature. The phase diagram is constructed by calculating the bubble points and dew points for a gas mixture
of interest.

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FIGURE 1. Two phase P-T plot for Gulf Coast gas

composition given in AGA Report 8.

the phase envelope is the two-phase region where the

hydrocarbon mixture will have components in both a gas
and liquid phase in varying proportions. The cricondenbar
for the gas mixture in Figure 1 is found at a temperature
of -61.2F and 953.5 psia. The cricondentherm in Figure
1 is found at a temperature of -21.9 F and 431.4 psia.
Note that if a gas mixture is kept at a temperature above
its cricondentherm, it will remain in a vapor phase only,
regardless of the pressure.

FIGURE 2. P-T plot of phase diagram for four

different gas compositions.

pressures and temperatures at or near pipeline operating

conditions.
Table 1. Gas Compositions used for phase diagrams
in Figure 2.
Gulf Coast
Component
Methane
Ethane
Propane
Isobutane
n-Butane
Isopentane
n-Pentane
n-Hexane
Carbon Dioxide
Nitrogen

The portion of the phase envelope below and to the left

of the critical point is referred to as the bubble point
curve. Pressure and temperature points that would plot
above and to the right of the critical point are referred to
as supercritical, or above the critical point. The supercritical region is also described as the dense phase region
because hydrocarbon density behavior in this region is
difficult to describe as gas or liquid only.

Mole %
96.5222
1.8186
0.4596
0.0977
0.1007
0.0473
0.0324
0.0664
0.5956
0.2595

Sample A
Sample B
(S. Louisiana) (Wyoming)
Mole %
Mole %
Mole %
90.6724
93.9139
86.6296
4.5279
2.8943
6.9470
0.828
1.1843
2.3997
0.1037
0.2915
0.6161
0.1563
0.3637
0.8876
0.0321
0.1423
0.4317
0.0443
0.1122
0.0000
0.0393
0.2234
0.1054
0.4676
0.2705
1.0690
3.1284
0.6041
0.9140

Amarillo

Regulator Staging and Sample System Heating

On-line chromatographs require a pressure reduction from
line pressure to a very low sample stream pressure. This
presents a new set of problems for most gas streams, because with pressure reduction there is a thermodynamic
Joule-Thomson cooling effect. This phenomenon may be
dealt with by multi-staging the pressure reductions and by
heating the gas stream and equipment prior to the pressure cuts. Keep in mind that using phase diagrams as a
design tool for the sample system may have a predictive
dew point temperature uncertainty of as much as 30F
[2],[3].

The part of the phase envelope to the right of the critical point defining the phase boundary is referred to as
the dew point curve. Dew points plotted between the cricondenbar and cricondentherm comprise a portion of the
retrograde region of the phase envelope. At pressures
and temperatures outside of the phase envelope, to the
right of the dew points, is where the hydrocarbon mixture
will exist as a gas.
The shape and size of the phase envelope is determined
by the composition of the hydrocarbon mixture. Figure 2
is a plot of four different gas compositions on the same
P-T plot.

Figure 3 depicts the phase diagram for a production gas

that is being taken either through a series of pressure reductions or a single pressure cut for sampling purposes.
Three pressure reduction paths are depicted. The first path
begins at 45F and 800 psia. Using the calculated Joule
Thomson (J-T) temperature change for a single pressure
reduction, it is apparent that some portion of the gas will
form liquids before reaching the desired chromatograph
sample pressure of 30 psia.

Gas compositions Gulf Coast and Amarillo do not have

as much pentanes plus heavier hydrocarbon fractions as
do Sample A and Sample B. Consequently their twophase region is smaller, and the opportunity to form liquids only exists at very low temperatures. This is not the
case however, for Sample A and Sample B gases which
might be typical of heavy hydrocarbon-rich production
gas. Note that liquid condensation is likely to occur at

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The second path depicts a single stage reduction through

a pressure reduction from a beginning temperature of
65F. This may be satisfactory at certain times in the year,
but condensation may possibly exist at other times; for
example, in the winter.

has high mole percentage amounts of ethane, butanes,

and isopentane.
Cricondentherm values are computed for each of the
gases in Table 2. One might note that the gas mixtures
having more of the heavier hydrocarbons such as hexane,
heptane and octane exhibit the highest value of cricondentherm. Gas mixtures having a high cricondentherm
value require special consideration during cold weather
conditions or when pressure reductions are required.

The third path demonstrates how the entire pressure cut

may be accomplished in three pressure reduction stages.
The three reductions stages are from 800 to 500 psia, 500
to 200 psia, and 200 to 30 psia. No heat is added to the
gas stream at each stage and the selection of pressure
reduction stages has avoided the two phase region of the
phase diagram. The results are satisfactory provided that
the beginning temperature is not less than about 35F.
This third path may not be satisfactory in the winter and
the ending temperature may not be satisfactory for the
analyzer applications if water vapor is a gas component.

Lumping of hydrocarbons that are heavier than hexane

is often referred to as the hexanes plus value. The assumed vs actual distribution of the heavier components
can affect the resulting calculation of the gas properties
and the hydrocarbon dewpoint. The hexane plus values in
Table 2 have been extended using an assumed hydrocarbon expansion relationship of 47% hexane, 36% heptane,
and 17% octane. Note that there is a significant difference
in the calculated cricondentherm.
Actual field measurements of the South Louisiana gas
mixture using a chilled mirror have indicated an operating
hydrocarbon dew point of 65F. This would indicate that
the pressure condition for the field measurement was very
close to the cricondentherm pressure. The actual operating temperature was 80F due to pipeline compression
discharge temperatures, but had the gas been allowed to
cool to ground temperature of 60F, we could expect that
hydrocarbon liquids would condense inside the pipe.

Considering the previous example it is very important

that the correctly proportioned hexane plus mole percent
assumptions match the actual blend in order to have an
accurate hydrocarbon dew point prediction. An extended
laboratory analysis of the gas to at least nonane is recommended to determine the correct ratios.
Figure 3. P-T Plot of phase diagram showing
pressure reduction paths for gas sampling
application.

FERC GAS TARIFF SPECIFICATIONS

Within the gas quality specifications in FERC gas transportation tariffs is a description of how hydrocarbon dew
point requirements are to be enforced. The first method
is to specify a discrete operating hydrocarbon dew point
value. This method requires that at all times the gas must
have a hydrocarbon dew point at the prevailing operating
pressure less than or equal to a specified value. It is common to see a value of 20F specified in tariffs.

GAS COMPOSITION AND HYDROCARBON DEW

POINT
Heating value is an important gas quality value that many
in the industry use to evaluate natural gas sources. Table 2 provides a comparison of five different natural gas
compositions. Two of these compositions are described
in AGA Report 8[1] and the other three are gas analyses
from various operations across the United States. It can be
seen by examining the calculated heating values in Table
2 that heating value cannot be used as a reliable predictor
of hydrocarbon dew point. The Appalachian gas blend has
a very high heating value, but a low cricondentherm.

Another approach is to specify a cricondentherm value for

which the gas mixture must be equal to or less than. This
approach also requires a specification of the particular
equations of state used to calculate the cricondentherm
and the hexanes plus ratio assumptions that would be applied to the calculation. The advantage of this method is
that field determinations of hydrocarbon dew point are not
required, but instead a molar analysis of a gas sample is
used to determine the dew point.

For the South Louisiana mixture the major contribution to

heating value is from the hexane plus heavier hydrocarbons and butane fractions in the mixture. The Appalachian
gas has been processed and contains small amounts of
constituents beyond propane, but has high amounts of
ethane and propane. By comparison, the Wyoming gas

A third approach to controlling hydrocarbon dew point

through specification in the FERC tariff is to specify the
permissible mole percentage of the pentane plus liquefiable portion of the gas mixture that would be acceptable.

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The pentane plus liquefiable portion of the gas specification assumes full processing of the gas stream and is
usually tailored to conditions that exist downstream of a
gas processing plant. This approach limits the plant operators options to not process gas in uneconomic market
conditions.

Most transportation pipelines require real time gas analysis and SCADA system analysis of analytical results. This
arrangement allows for system computation of the mainline gas composition and identification of the potential for
formation of hydrocarbon condensates. This approach
also allows the operating company the opportunity to
communicate about out of specification conditions with
downstream customers and actions they are taking to resolve the concern.

TARIFF SPECIFICATIONS ENFORCEMENT

When gas is found to be out of specification with tariff
requirements enforcement actions must be taken by the
operating pipeline. The enforcement options available include extending a waiver to the delivering party if it will
not affect downstream commercial operations, requiring
a remedy of the out of specification condition, or simply
shutting in the gas receipt.

CONCLUSIONS
In this discussion we have described phase diagrams, elements of the phase diagram and uses of these diagrams
for determining when an operating condition is near the
hydrocarbon dew point. We have considered different gas
mixtures found in the gas industry and their unique hydrocarbon dew point characteristics. We have discussed how
pressure reductions may be made without formation of
hydrocarbon liquids, and we have discussed how hydrocarbon dew point is specified and enforced in the natural
gas industry. This paper was intended to be introductory
in nature and if the reader is interested, further study in
organic chemistry, thermodynamics, and gas processing
is encouraged.

In a supply rich environment, refusing to accept the gas

delivery is a possible solution. Another option is to require
processing of the gas. Otherwise, processing may be
done through an existing downstream processing plant or
by installing a gas processing assembly such as a Joule
Thomson process unit, or a turbo expander plant.
The waiver concept requires assurance of pairing of lean
gas sources such that the blended gas composition is
within the required specifications.

Table 2 Comparison of Natural Gas Molar Compositions (mole %) with Computed Heating Value, Relative
Density, and Cricondentherm.

Methane
Nitrogen
Carbon Dioxide
Ethane
Propane
Isobutane
Normal Butane
Isopentane
Normal Pentane
Hexane
Heptane
Octane
Gross HV at Pb, Tb
Real Gas Relative
Density
Cricondentherm ( F)

Amarillo
(extended)

South
Louisiana
93.9137
0.6041
0.2705
2.8943
1.1843
0.2915
0.3637
0.1423
0.1122
0.2234

1034.8

90.6724
3.1284
0.4676
4.5279
0.8280
0.1037
0.1563
0.0321
0.0443
0.0185
0.0141
0.0067
1035.1

1076.7

South
Louisiana
(extended)
93.9137
0.6041
0.2705
2.8943
1.1843
0.2915
0.3637
0.1423
0.1122
0.1050
0.0804
0.0380
1077.9

0.6086
-25.5

0.6088
6.1

0.6056
27.6

0.6063
63.7

Gulf
Coast

Gulf Coast
(extended)

96.5222
0.2595
0.5956
1.8186
0.4596
0.0977
0.1007
0.0473
0.0324
0.0664

90.6724
3.1284
0.4676
4.5279
0.8280
0.1037
0.1563
0.0321
0.0443
0.0393

1036.1

96.5222
0.2595
0.5956
1.8186
0.4596
0.0977
0.1007
0.0473
0.0324
0.0312
0.0239
0.0113
1036.4

0.5810
-19.2

0.5813
19.1

Amarillo

REFERENCES
Compressibility Factors of Natural Gas and Other Related Hydrocarbon Gases, Transmission Measurement
Committee Report 8, July 1994.

Wyoming
(extended)

Appalachian
79.8500
0.2595
0.5956
17.0000
2.0004
0.0977
0.1007
0.0473
0.0224
0.0264

1135.4

86.6295
0.9140
1.0690
6.9470
2.3997
0.6161
0.8876
0.4317
0.0000
0.0495
0.0379
0.0179
1135.9

1174.4

Appalachian
(extended)
79.8500
0.2595
0.5956
17.0000
2.0004
0.0977
0.1007
0.0473
0.0224
0.0124
0.0095
0.0045
1174.5

0.6592
29.2

0.6596
47.8

0.6690
-13.9

0.6691
0.0

Wyoming
86.6295
0.9140
1.0690
6.9470
2.3997
0.6161
0.8876
0.4317
0.0000
0.1054

Obtaining Natural Gas Samples for Analysis by Gas

Chromatography, Gas Processors Association Publication, GPA 2166-05, 2005.

Collecting and Handling of Natural Gas Samples for

Custody Transfer, American Petroleum Institute, Manual
of Petroleum Measurement Standards, Chapter 14, Section 1, 2002.

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