Study compares C6+

characterization methods for

natural gas phase envelopes
11/21/2005

A recent study applied different C6+ characterization techniques to generate a phase

envelope for natural gases and, using these techniques and a single dewpoint
measurement, generated a relatively correct phase envelope.
Using the single dewpoint measurement, we determined the appropriate component or
cut distribution for C6+ and evaluated the accuracy of each method for two case studies
covering rich and lean natural gases.
We evaluated the effect of four C6+ characterization techniques for generating phase
envelopes for natural gases. With these techniques, a single dewpoint measurement
was used to generate a relatively correct phase envelope.
Using the single dewpoint measurement, we determined the appropriate component or
cut distribution for C6+ by adjusting the C6+ properties such as molecular weight, critical
temperature, etc.
The exponential decay, or logarithmic, distribution of C 6+ will improve the prediction
accuracy of potential hydrocarbon liquid content estimations by use of a C 6+ molecular
weight to match a single dewpoint. This approach is internally consistent and results in
generation of relatively accurate phase behavior.
For a sound process design or operation, we suggest using at least one experimental
saturation measurement such as a dewpoint or bubblepoint near the potential
operating conditions to characterize the heavy ends. Once the characterization is
established, one should use additional experimental measurements to verify the
accuracy and validity of the tuning technique.
Phase diagrams

In facilities operations, the understanding of where the process is on a phase diagram

can often help the engineer and operator avoid design and operating mistakes. The oil
and gas industry is full of many war stories about phase diagram disasters. Most
instances are never related back to the phase diagram misunderstanding.
In one well-documented but poorly published case, a dry gas pipeline that was pigged
flooded miles of sandy beach. In another case, thousands of kilowatts of compression

power were installed to maintain the pressure of a reservoir above the dewpoint when
in fact the reservoir was at a temperature above the cricondentherm.
Equipment manufacturers and gas purchasers have often made specifications for
superheat or dewpoint that have not been met and led to upset customers or millions
of dollars of lawsuits.
One of the first issues that a gas plant or gas production facility engineer must resolve
should be: Where is the process operating with respect to the phase diagram? A
general knowledge, if not a detailed knowledge, will allow the design engineer and the
facilities operator to make intelligent decisions that significantly affect the profitability of
a gas production plant.
The phase envelope has many applications in petroleum production and process
design ranging from reservoir simulation, pumping liquids, transportation of natural gas
by pipeline or in LNG form, ethane and heavier recovery, refrigeration processes, and
operation near the critical point or in the supercritical region. A sound process design
requires a good knowledge of the phase envelope. 1

For a petroleum fluid, one can construct a phase envelope using experimental
measurements of a series of bubblepoints and dewpoints. This, however, is very time
consuming and expensive. With a little care and experience, an accurate phase
envelope can be constructed with an equation of state based on a limited number of
experimental measurements.1 2
In many cases, real fluid mixtures consist of dozens, if not hundreds, of components.
Attempting to consider all of the components present in such a mixture is impractical
because experimental determination of each component may not be feasible or
possible.
More importantly, the vapor-liquid equilibrium calculations for systems containing many
components would be time consuming. The required calculation time increases
exponentially with the number of components in the mixture. To overcome this
difficulty, the components heavier than hexane and their derivatives are normally

lumped together as one or more pseudocomponents called the heavy ends, C 6+,or
C7+.1
There are many references that describe techniques for characterizing C 6+ fractions.1-6
The C6+ fraction is frequently the determining factor in defining the dewpoint of the gas.
Liquid formation in a natural gas pipeline changes the line pressure drop and flow
characteristics. A seemingly inconsequential amount of liquid can cause significant
changes in line pressure drop or capacity (OGJ, Feb. 4, 2002, p. 56). 7
This article presents and briefly describes several methods of heavy-ends
characterization, checks the accuracy of each method, and presents tips to improve
the accuracy of each method. We also included a recent method for characterizing
heavy ends described by Starling to generate a more accurate phase envelope for
natural gases.8
This technique uses a single experimentally measured dewpoint and assumes a
logarithmic distribution, presented by Katz, 9 of nC6H14 to nC17H36 for heavy ends. This
technique has been verified by matching the potential hydrocarbon liquid content
(PHLC) of the gas. The PHLC is expressed in terms of mg of liquid/cu m of gas at 0
C. and 101.325 kPa.
Case Study 1

Table 1 shows the composition of a rich gas in the first two columns.

This rich gas contains 3.1 mole % C7+ with a molecular weight of 132 and a specific
gravity of 0.774. The experimentally measured dewpoint pressure is 4,075.6 psia at

180.4 F.10 This case study will use the Peng-Robinson equation of state; 11 the SoaveRedlich-Kwong equation of state gives similar results.
We used four different methods to characterize the C 7+ components:
Method A. This method treats C7+ as a single cut. Based on its molecular weight and
specific gravity, we predicted its normal boiling point (317.2 F.), critical temperature
(Tc = 645.2 F.), critical pressure (Pc = 371.6 psia), and acentric factor ( = 0.425574)
using correlations similar to the ones by Riazi and Daubert. 12
The predicted dewpoint pressure is 3,433 psia-far away from the measured value of
4,076 psia.

Fig. 1 shows the predicted phase envelope for this method. This envelope does not
pass through the measured dewpoint.
Method B. This method breaks the C7+ into 11 single carbon numbers (SCNs) ranging
from SCN 7 to SCN 17+ using the exponential decay procedure presented by Katz and
applied by others.9 13 We used generalized SCN properties as reported by Whitson. 14
Table 1 shows the resulting distributions.
The predicted dewpoint pressure is 4,030 psia, which is relatively accurate. Fig. 1
shows that the corresponding phase envelope almost passes through the measured
dewpoint.

 Method C. This method lumps the 11 SCN components of Method B into four cuts.
Table 1 also shows these cuts and compositions. The predicted dewpoint pressure is
3,885 psia. Fig. 1 shows the corresponding phase envelope.
Method D. This method is similar to Method B, except that we used 12 normal
paraffins (alkanes) instead of SCN components to represent the C 6+ components. The
predicted dewpoint pressure is 3,730 psia and Fig. 1 also shows the corresponding
phase envelope.
The advantage of this method is that n-alkane components are readily available in
many commercial software packages whereas the SCNs may not be.
Fig. 1 shows that none of the methods (except method B which comes close) matches
the experimentally measured dewpoint. The next section shows how the prediction of
each method can be improved to match the experimentally measured dewpoint.
Adjusting molecular weight

For Method A, by changing the molecular weight of C 7+ to 152.5, we can match

perfectly the measured dewpoint (Fig. 2). Based on a molecular weight of 152.5 and a
specific gravity of 0.774, the new values for the estimated properties will be

NBP = 381 F.
Pc = 308.4 psia.

 Tc = 706.9 F.
= 0.468456.
An alternative option is to adjust only Tc to 703.5 F. Again, the tuned Tc makes the
phase envelope pass through the measured dewpoint (Fig. 2). The Tc adjustment is
preferred because less work is involved.
Tuning interaction parameter

For Methods B and C, one can adjust the binary interaction parameter, k ij. The
accompanying box shows a common correlation to estimate the binary interaction
parameter.
In this equation, Vci and Vcj represent the critical volumes of components i and j,
respectively. The default value of exponent n is normally set to 1.2, but it can be used
as a tuning parameter to match the experimentally measured dewpoint.
For our case study, we obtained n = 1.3011 for Method B and n = 1.6573 for Method C.
Fig. 2 shows the resulting phase envelopes for these two methods.
Method D mole wt tuning

The distribution (i.e., the mole %) of the alkane part of C 6+ depends on the assumed
value of the C6+ molecular weight. Fig. 2 shows that, by changing the molecular weight
of C7+ to 154, we can match perfectly the measured dewpoint.
Fig. 2 shows that all of the generated (tuned) phase envelopes pass through the
measured dewpoint; but they have different cricondentherm points. Are all of these
phase envelopes correct?
We performed Case Study 2 to answer this question.
Case Study 2

Table 2 shows the composition of a lean natural gas that we used in Case Study 2.
This lean gas contains only 0.067 mole % C6+. Even though the amount of C6+ is small,
it has a large impact on the condensate.

Table 2 (first two columns) shows the detailed laboratory analyses 15 of C6+. We
calculated the C6+ components to have a molecular weight of 94.12, a specific gravity
of 0.738, and an NBP of 195 F. using the Soave-Redlich-Kwong equation of state. 16
For this case, all other calculations were performed with the Soave-Redlich-Kwong
equation of state.
We plotted the experimentally measured PHLC at 594.7 psia as a function of
temperature in Fig. 1; extrapolation yielded a dewpoint temperature of 52.1 F. We
used the methods from Case Study 1 to characterize the C 6+ by matching the
experimentally determined dewpoint.

Table 2 presents the tuned molecular weight and distribution of components for each
method. Figs. 3 and 4 show the predicted PHLC as a function of temperature and the
phase envelope, respectively. The cricondentherm for the lumped C 6+ method was
below 15 F.; therefore, we predicted zero values for PHLC.

Fig. 4 shows that three of the characterization methods generated practically the same
phase envelope. But do all of these characterization methods present the true phase
behavior of this lean gas? The answer is yes and no.

Fig. 3 indicates that, for temperatures close to the dewpoint, all three methods predict
PHLCs close to the experimental values; however, at lower temperatures (about 20
F.) the deviation from experimental values increases. Only the normal alkane
distribution method gives accurate values even at lower temperatures.

For this lean gas, Fig. 5 shows the complete phase envelope containing the hydrate
curves, with and without inhibitor, a 95% quality line, and the retrograde curve for
which C6+ is distributed based on n-alkanes.
Acknowledgment

The authors appreciate the support provided by John M. Campbell & Co. and
Chemical Engineering Consultants Inc. We also acknowledge that the calculations
were performed with WinProp (Computer Modeling Group), EzThermo (Moshfeghian &
Maddox), and Gcap (John M. Campbell & Co.).
References

1. Maddox, R.N., and Lilly, L.L., Gas Conditioning and Processing, Volume 3:
Advanced Techniques and Applications, Norman, Okla.: John M. Campbell & Co.,
1994.

2. Nasrifar, K., Bolland, O., and Moshfeghian, M., Predicting Natural Gas Dew Points
from 15 Equations of State, Journal of Energy and Fuel, Vol. 19 (2005), pp. 561-72.