Fluid Phase Equilibria 228–229 (2005) 213–221

Advanced equation of state method for modeling TEG–water

for glycol gas dehydration
Chorng H. Twua∗ , Vince Tassoneb , Wayne D. Simb , Suphat Watanasiric
a Aspen Technology, Inc., 2811 Loganberry Court, Fullerton, CA 92835, USA
b Aspen Technology, Inc., Suite 900, 125 9th Avenue SE, Calgary, Alta., Canada T2G 0P6
c Aspen Technology, Inc., Ten Canal Park, Cambridge, MA 02141, USA

Abstract

An advanced equation of state has been developed for modeling triethylene glycol (TEG)–water system for glycol gas dehydration process.
The dehydration of natural gas is very important in the gas processing industry. It is necessary to remove water vapor present in a gas stream
that may cause hydrate formation at low-temperature conditions that may plug the valves and fittings in gas pipelines. In addition, water
vapor may cause corrosion difficulties when it reacts with hydrogen sulfide or carbon dioxide commonly present in gas streams. The most
effective practice to remove water from natural gas streams is to use TEG in the gas dehydration process. In modeling such a process, it is
crucial that the phase behavior of the TEG–water–natural gas system is correctly modeled, with methane being the predominant component
in natural gas. Of the three binaries, methane–water, methane–TEG and TEG–water, the methane binaries can be adequately modeled by
an equation of state, e.g. [J.R. Cunningham, J.E. Coon, C.H. Twu, Estimation of aromatic hydrocarbon emissions from glycol dehydration
units using process simulation, in: Proceedings of the 72nd Annual Gas Processors Association Convention, San Antonio, TX, March 15–17,
1993]. For the TEG–water binary, the Parrish’s empirical hyperbolic correlation [W.R. Parrish, K.W. Won, M.E. Baltatu, Phase behavior of the
triethylene glycol–water system and dehydration/regeneration design for extremely low dew point requirements, in: Proceedings of the 65th
Annual GPA Convention, San Antonio, TX, March 10–12, 1986] is recommended by GPSA [GPSA Engineering Data Book, 10th ed., First
Revision, Gas Processors Suppliers Association, Tulsa, OK, 1994] and is currently widely used in the industry. In this work, we applied the
TST (Twu–Sim–Tassone) equation of state to model this binary system. A methodology was also developed to determine the water dew point
and calculate water content for this system. The TST equation of state is shown to accurately represent the activity coefficients of TEG–water
solutions as well as water dew point temperatures and water content of gas over the entire application range of temperature, pressure and
concentration encountered in a typical TEG dehydration unit.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Triethylene glycol; Water; Water dew point; Water content; CEoS; TST; Cubic equation of state; Excess energy mixing rule; Activity coefficient;
Gas dehydration

1. Introduction ural gas dehydration is by absorption of water using TEG.

The dehydration of natural gas is an important operation
in the gas processing industry. The standard method for nat-
∗
Corresponding author. Tel.: +1 403 303 1000; fax: +1 403 303 0914.
E-mail addresses: chorng.twu@aspentech.com (C.H. Twu),
vince.tassone@aspentech.com (V. Tassone), wayne.sim@aspentech.com
(W.D. Sim), suphat.watanasiri@aspentech.com (S. Watanasiri).
Glycol dehydration units typically consist of a contactor, a
flash tank, heat exchangers and a regenerator. The lean TEG
liquid stream enters at the top of the absorber or the contactor
while the natural gas stream containing water to be removed
(wet gas) enters at the bottom of the absorber. The lean TEG
liquid absorbs water as it progresses toward the bottom of the
column. A dry gas exits at the top of the absorber. The rich
TEG stream is sent to the regenerator where water is removed
and the lean TEG liquid is returned to the absorber.

0378-3812/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.09.031
214 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221
The most important aspect of modeling any dehydration
unit is to correctly model the methane–glycol–water ternary
[1]. This ternary controls the predicted glycol circulation
rates, purities of the lean glycol and the water content of the
dry gas. Of the three binaries, methane–water, methane–TEG
and TEG–water, the methane binaries can be adequately mod-
eled by an equation of state (e.g. [1]). At one time, only
graphical data from vendors were available in the literature
to model the TEG–water binary. These data often were in
disagreement at low water concentration portion resulting in
confusion.
Since the concentration of water in the natural gas is typi-
cally low, less than 0.2 mol%, and the concentration of TEG in
the lean TEG solution is high, normally higher than 98 wt.%,
highly concentrated TEG solutions higher than 99.50 wt.%
are usually required if the water concentration in the effluent
gas stream is specified to be very low. Therefore, in order to
have an accurate design of a dehydration unit, vapor–liquid
equilibrium data for TEG–water need to be accurate, espe-
cially in the dilute region of water. Parrish et al. [2] gave
an extensive review of the available equilibrium data. Based
on the data reviewed, they found the data of Herskowitz and
Gottlieb [4] to be the most reliable.
Herskowitz and Gottlieb [4] measured the activity coef-
ficients of water in TEG at two temperatures, 297.60 and
332.60 K. The lowest mole fraction of water for which ac-
tivities were measured was 0.1938 and 0.2961 at 297.60 and
332.60 K, respectively. They fit their measured activity coef-
ficients to the van Laar equation. They did not measure data
in the infinite dilution region. In order to predict the equilib-
rium behavior in the infinite dilution region, most researchers
simply extrapolated the measured data at low water concen-
trations to infinite dilution using an activity coefficient model
such as van Laar. However, extrapolating the van Laar, or any
other activity coefficient model will yield erroneous results
for the infinite dilution activity coefficients.
To help better define the TEG–water system, Parrish et
al. [2] measured activity coefficients at infinite dilution as a
function of temperature. These data, shown in Fig. 1, were
used to evaluate the existing data. The data of Herskowitz
and Gottlieb [4] were found to be in good agreement with the
measured infinite dilution activity coefficient data.
Bestani and Shing [5] subsequently measured activity co-
efficients of water in TEG at infinite dilution, but their data
are 13–17% higher than those of Parrish as shown in Fig. 1.
Based on the Bestani extrapolation method to 477.15 K, the
predicted water activity coefficient is above 1.0. A value of
water activity coefficient that is greater than unity at 477.15 K
implies that TEG would be a poor dehydrating agent at around
this temperature, which is contrary to plant experience [6].
Therefore, Bestani data are not used in this work.
Parrish et al. [2] combined their infinite dilution activity
coefficients data with the finite-concentration activity coef-
ficients of Herskowitz and Gottlieb and then fit them to the
activity coefficient model of a four-suffix Margules equation
over the entire range of composition at each temperature for
Fig. 1. Infinite dilution activity coefficient of water in water–TEG system:
(
) Exp., Parrish et al. [2]; () Exp., Bestani and Shing [5]; (—) this work;
(- - -) Parrish et al. [2].
the TEG–water system. However, since the Margules activity
coefficient model is unable to fit the activity coefficients over
an extended temperature range for process design calcula-
tions, Parrish et al. proposed an empirical hyperbolic equa-
tion to predict the activity coefficients of TEG (1) and water
(2) over the entire range of temperatures and compositions:
B2 ln[cosh(τ)] x2 B tanh(τ)
ln γ1 = − − Cx22 (1)
A x1
ln γ2 = B[tanh(τ) − 1] − Cx12 (2)
where
Ax2
τ= (3)
Bx1
and tanh and cosh are hyperbolic tangent and cosine func-
tions. The subscript number represents component: 1 for TEG
and 2 for water. A, B, and C are temperature-dependent pa-
rameters:
A = exp(−12.792 + 0.03293T ) (4)
B = exp(0.77377 − 0.00695T ) (5)
C = 0.88874 − 0.001915T (6)
where T is the temperature in Kelvin.
Both Herskowitz and Gottlieb, and Parrish used activity
coefficient models to fit the activity coefficient data as a func-
tion of mole fraction and temperature. However, using an
activity coefficient model to describe the liquid phase still
requires the use of an equation of state to handle the non-
ideality of the gas phase and a Poynting correction factor to
account for the effect of pressure. In addition, the standard
state fugacity as a function of temperature ranging from the
temperatures below 273.15 K to critical temperature need to
be correlated for water for the TEG gas dehydration. Since
different models are used for vapor and liquid, the approach
has limitations. For example, no critical conditions can be
calculated, the K-values near critical region is not reliable,
 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221 215

other thermodynamic properties such as density cannot be The TST cubic equation of state is represented by the
calculated, modeling light gases requires the use of Henry’s following equation:
law constants, etc. Besides, the results of extrapolation to
RT a
high temperatures and high pressures may not be reliable. P= − (7)
For example, using the van Laar equation with the given bi- v − b v2 + 2.5bv − 1.5b2
nary interaction parameters from Herskowitz and Gottlieb for Eq. (7) can be rewritten in another form as
extrapolation to 477.15 K, the van Laar predicts a water activ-
RT a
ity coefficient of 1.1. As mentioned earlier in the analysis of P= − (8)
Bestani and Shing data, a value of water activity coefficient v − b (v + 3b)(v − 0.5b)
that is greater than unity is not realistic. Using the empirical The values of a and b at the critical temperature are found
hyperbolic function of Parrish, a water activity coefficient of by setting the first and second derivatives of pressure with
0.9477 is obtained at 477.15 K, which is below unity, but is respect to volume to zero at the critical point resulting in
still too high. The activity coefficient of water at this tem-
perature is expected to be below 0.80 [6]. Furthermore, Eqs. R2 Tc2
ac = 0.470507 (9)
(1) and (3) contain mole fraction of component 1, x1 , in the Pc
denominator. These equations will break down when x1 ap- RTc
proaches zero. Although the TEG mole fraction is unlikely bc = 0.0740740 (10)
Pc
to be zero in practical natural gas dehydration process, it is
a notable deficiency that engineers should be aware of. The Zc = 0.296296 (11)
Parrish’s correlation is recommended by the GPSA [3] and
is currently widely used in the industry. where subscript c denotes the critical point. It is noted
In this work, we applied the TST (Twu–Sim–Tassone) that the values of Zc from the Soave–Redlich–Kwong [9]
equation of state model [7,8] to describe the phase behavior and Peng–Robinson [10] models are both larger than 0.3
of the TEG–water system. We also presented a methodology (0.333333 and 0.307401, respectively), but that for TST is
to determine water dew point and calculate water content for slightly below 0.3, which is closer to the typical value of Zc
this system. The TST equation of state represents accurately for most compounds.
the activity coefficients for water and TEG, the water dew The parameter a is a function of temperature. The value
point temperatures and water content over the entire range of a at any temperature a(T) can be calculated from
of temperature, pressure and composition encountered in a a(T ) = α(T )ac (12)
typical TEG dehydration unit.
where the alpha function, α(T), is a function only of reduced
temperature, Tr = T/Tc . We use the Twu alpha function [11]:
2. Advanced TST (Twu–Sim–Tassone) equation of NM )
state model α = TrN(M−1) eL(1−Tr (13)
Eq. (13) has three parameters, L, M and N. These parameters
Twu, Sim and Tassone (TST) recently developed CEoS/AE
are unique to each component and are determined from the
mixing rules [7,8] that permit a smooth transition of the mix-
regression of pure component vapor pressure data. Table 1
ing rules to the conventional van der Waal’s one-fluid mixing
lists the L, M and N parameters for TEG and water for use
rules. They also proposed a cubic equation of state for bet-
with the TST equation of state in this paper. The values of L,
ter handling of polar and heavy components and a GE model,
M and N for N2 , CO2 , H2 S and light hydrocarbons in natural
which when combined with the CEoS/AE mixing rules allows
gas from methane to n-decane are also included in the table
both a van der Waal’s fluid and highly non-ideal mixtures to
for future applications.
be described over a broad range of temperatures and pres-
The TST zero-pressure mixing rules for the mixture a and
sures in a consistent and unified framework. It is extremely
b parameters are
desirable to have the CEoS/AE mixing rules reduce to the

 
classical quadratic mixing rules because the classical mixing a ∗ A E A E
1
rules work very well for nonpolar and slightly polar systems. a∗ = b∗ vdw ∗ + 0
− 0vdw (14)
bvdw Cr RT RT
Introducing this capability into an excess energy model en-
sures that the binary interaction parameters for the classical b = bvdw (15)
mixing rules available in many existing databanks for sys-
tems involving hydrocarbons and gases can be used directly The parameters a* and b* in Eq. (14) are defined as
in the new excess energy mixing rules. In other words, it Pa
allows the equation of state to describe some binaries in a a∗ = (16)
R2 T 2
multi-component mixture using the van der Waal’s one-fluid
mixing rules, while other pairs with more non-ideal interac- Pb
b∗ = (17)
tions are described by the excess energy mixing rules. RT
216 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221

Table 1
L, M and N parameters of Twu α function with the TST CEoS
ID Component Tc (K) Pc (kPa) L M N
1 TEG 769.50 3320.00 0.196667 0.863521 5.10947
2 H2 O 647.13 22055.00 0.430058 0.870932 1.67211
3 N2 126.20 3400.00 0.0649944 0.892385 2.34000
4 CO2 304.21 7383.00 0.945951 0.888652 0.65000
5 H2 S 373.53 8962.90 0.231877 0.784346 1.12000
6 CH4 190.564 4599.00 0.0813821 0.905296 2.13000
7 C2 305.32 4872.00 0.147335 0.879706 1.98500
8 C3 369.83 4248.00 0.172517 0.879570 2.20000
9 NC4 425.12 3796.00 0.515633 0.846523 1.02632
10 NC5 469.70 3370.00 0.385772 0.817594 1.35710
11 NC6 507.60 3025.00 0.119904 0.858552 3.17252
12 NC7 540.20 2740.00 0.658164 0.829578 1.11729
13 NC8 568.70 2490.00 0.486147 0.809629 1.49823
14 NC9 594.60 2290.00 0.477371 0.796573 1.58848
15 NC10 617.70 2110.00 0.436564 0.800707 1.82508

 
Note that the temperature-independent van der Waal’s mixing 1
rule bvdw is used for the b parameter in Eq. (15). The expres- bvdw = xi xj (bi + bj ) (22)
2
i j
sion of bvdw is given below in Eq. (22). The TST zero-pressure
mixing rules assume that AE0vdw , the excess Helmholtz energy Since AE0 in these equations is at zero pressure, its value is
of van der Waal’s fluid at zero pressure, can be approximated
identical to the excess Gibbs free energy GE at zero pressure.
by AE∞vdw , the excess Helmholtz energy of van der Waal’s
Therefore, any activity model such as the NRTL equation
fluid at infinite pressure:
can be used directly for the excess Helmholtz free energy

 expression AE0 in Eq. (14).
AE0vdw AE∞vdw ∗
avdw  a∗
i
= = C1 ∗ − xi ∗ (18) The TST zero-pressure mixing rule assumes that the ex-
RT RT bvdw bi cess Helmholtz free energy of the van der Waal’s fluid (AE0vdw ,
i
Eq. (18)) is independent of pressure. This approximation is
With this assumption, the zero-pressure mixing rule transi-
required to allow a smooth transition to the conventional van
tions smoothly to the conventional van der Waal’s one-fluid
der Waal’s one-fluid mixing rule. Therefore, a binary interac-
mixing rule. The C1 in Eq. (18) is a constant and is defined
tion parameter kij is introduced in Eq. (21) to correct for this
as
approximation. In this work, kij is not needed to adequately
 
1 1+w fit the TEG–water VLE data and is set equal to zero.
C1 = − ln (19) Twu et al. [7,8] proposed a multi-component equation for a
(w − u) 1+u
liquid activity model for use in the TST excess energy mixing
where u and w are equation-of-state-dependent constants rules:
used to represent a general two-parameter cubic equation of n
n
GE  j xj τji Gji
state. For the TST equation of state, u is 3 and w is −0.5 as = xi
n (23)
shown in Eq. (8). RT k xk Gki
i
Cr in Eq. (14) is a function of a parameter r, which is the
reduced liquid volume at zero pressure: Eq. (23) has the same functional form as the NRTL equa-
  tion, but there is a fundamental difference between them.
1 r+w NRTL assumes that Aij , Aji and αij are the parameters of the
Cr = − ln (20)
w−u r+u model, but the excess Gibbs energy model proposed by Twu
et al. [7,8] assumes that τ ij and Gij are the binary interaction
The value of r = 1.18 is recommended by Twu et al. [12]. parameters. More importantly, any appropriate temperature-
Using r = 1.18, Cr = −0.518850 is used in this work. dependent function can be applied to τ ij and Gij . For example,
AE∞ and AE0 in above equations are the excess Helmholtz to obtain the NRTL model, τ ji and Gji are calculated as usual
free energies at infinite pressure and zero pressure, respec- from the NRTL parameters Aji , Aij and αji :
tively. The subscript vdw in AE∞vdw and AE0vdw denotes that
the properties are evaluated from the cubic equation of state Aji
τji = (24)
using the van der Waal’s mixing rule for its a and b parame- T
ters, avdw and bvdw :
Gji = exp(−αji τji ) (25)
 √
avdw = xi xj ai aj (1 − kij ) (21) In this way, the NRTL parameters reported in the DECHEMA
i j Chemistry Data Series can be used directly in our mixing
 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221 217

Table 2 Table 3
Binary interaction parameters for use in TST zero-pressure mixing rule Comparison of Parrish et al. [2] measured infinite dilution activity coeffi-
Binary TEG(1)/H2 O(2) cients of water (2) in TEG (1) solution with those calculated using TST
CEoS and Parrish’s hyperbolic equation
A12 −141.490
T (K) γ2∞ (measured) This work Parrish et al. [2]
A21 158.166
B12 0.254489 γ2∞ (calc.) Devi% γ2∞ (calc.) Devi%
B21 5.83380
α12 0.278879 300.43 0.5510 0.5565 0.99 0.5587 1.40
311.71 0.575 0.5773 0.41 0.5826 1.32
323.26 0.5900 0.5979 1.34 0.6072 2.91
rule and there is no difference between NRTL model and our 333.76 0.6170 0.6159 −0.19 0.6296 2.04
343.43 0.6240 0.6318 1.25 0.6503 4.21
model in the prediction of phase equilibrium calculations.
355.93 0.6360 0.6515 2.44 0.6772 6.47
We also note that Eq. (23) can recover the conventional 364.93 0.6690 0.6651 −0.58 0.6966 4.13
van der Waal’s mixing rules when the following expressions 378.32 0.6920 0.6845 −1.08 0.7257 4.87
are used for τ ji and Gji : AAD% 1.03 3.42
τji = 2 δij bi
1
(26)
bj error of ±1.03%. Parrish’s model systematically overpredicts
Gji = (27) the data with a positive average error of +3.42%. Fig. 1 also
bi indicates that Eq. (2) represents data at low temperatures bet-
where ter than those at higher temperatures. The TST EoS, on the

 √ √ 2 √ √  other hand, more accurately fits the data over the entire tem-
C1 ai aj ai aj
δij = − − + 2kij (28) perature range.
RT bi bj bi bj Table 4 shows the finite-concentration activity coefficients
of water in TEG measured by Herskowitz and Gottlieb as
Eqs. (26) and (27) are expressed in terms of cubic equation
functions of temperature and composition. For comparison,
of state parameters ai and bi , and the binary interaction pa-
the table again includes results from this work and those using
rameter kij . The above discussion demonstrates that Eq. (23)
Eq. (2). Data in Table 4 are also shown graphically in Fig. 2.
is more generic in its form than the NRTL model. Both the
Reviewing Fig. 2, it is observed that the data of Herskowitz
NRTL and van der Waal’s one-fluid mixing rule are special
and Gottlieb are not quite consistent with the data of Parrish.
cases of our excess Gibbs free energy function.
Due to the curvature of Herskowitz data, the extrapolation to
water mole fraction of zero (i.e., TEG mole fraction of 1.0)
will give infinite dilution activity coefficients of water in TEG
3. Correlation of activity coefficients
of about 0.65 at 297 K. This is much larger than the infinite
dilution activity coefficient data of Parrish at the same tem-
The TST equation of state and mixing rules described in
perature (<0.55). Since both the TST EoS and Eq. (2) fit the
the previous section are used to correlate the infinite dilution
infinite dilution activity coefficient data well, the fit to Her-
activity coefficient data of Parrish et al. [2] and the finite-
skowitz and Gottlieb data at high TEG concentration is quite
concentration activity coefficients of Herskowitz and Gottlieb
[4]. To cover the entire application range of temperature, Eq.
(24) is modified to include a temperature-dependent binary
interaction parameter Bji as follows:
Aji + Bji T
τji = (29)
T
where T is the temperature in K. The unit of Aji is in K and
Bji is dimensionless.
Table 2 lists the values of the binary interaction parameters
Aij , Aji , Bij , Bji and αij obtained for the TEG–water system.
Table 3 compares measured and calculated infinite dilution
activity coefficients of water in TEG as a function of temper-
ature. Also shown in the table are the infinite dilution activity
coefficients calculated from Parrish’s empirical hyperbolic
equation (Eq. (2)) for comparison. Data in Table 3 are also
shown graphically in Fig. 1. Results shown in Table 3 and
Fig. 1 indicate that the TST equation of state can accurately Fig. 2. Activity coefficient of water vs. liquid mole fraction TEG. Exp.,
correlate the infinite dilution activity coefficients of water in Herskowitz and Gottlieb [4]: (
) T = 297.6 K, () T = 332.6 K; (—) this
TEG covering a wide range of temperature with an average work; (- - -) Parrish et al. [2].
218 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221

Table 4
Comparison of Herskowitz and Gottlieb [4] measured activity coefficients of water (2) in TEG (1) solution with those calculated using TST CEoS and Parrish’s
hyperbolic equation
T (K) X (1) γ 2 (measured) This work Parrish et al. [2]

γ 2 (calc.) Devi% γ 2 (calc.) Devi%

297.60 0.8062 0.6604 0.6299 −4.62 0.6255 −5.28
297.60 0.7838 0.6640 0.6394 −3.71 0.6338 −4.55
297.60 0.6731 0.6760 0.6875 1.71 0.6742 −0.26
297.60 0.6731 0.6871 0.6875 0.06 0.6742 −1.87
297.60 0.5809 0.7062 0.7290 3.23 0.7078 0.22
297.60 0.5449 0.7201 0.7456 3.54 0.7210 0.13
297.60 0.5001 0.7407 0.7664 3.47 0.7378 −0.40
297.60 0.4967 0.7371 0.7680 4.19 0.7390 0.26
297.60 0.3996 0.7823 0.8138 4.02 0.7777 −0.58
297.60 0.3898 0.7876 0.8184 3.91 0.7819 −0.72
297.60 0.3057 0.8264 0.8585 3.89 0.8220 −0.53
297.60 0.2505 0.8608 0.8849 2.80 0.8545 −0.74
297.60 0.2187 0.8784 0.9000 2.46 0.8765 −0.22
297.60 0.1894 0.8994 0.9139 1.62 0.8994 0.00
297.60 0.1657 0.9177 0.9252 0.82 0.9198 0.23
297.60 0.1575 0.9225 0.9292 0.72 0.9272 0.51
297.60 0.1157 0.9507 0.9494 −0.13 0.9649 1.50
297.60 0.1077 0.9526 0.9534 0.08 0.9716 1.99
297.60 0.1051 0.9542 0.9547 0.05 0.9736 2.04
297.60 0.1026 0.9563 0.9559 −0.04 0.9756 2.01
297.60 0.0657 0.9802 0.9745 −0.58 0.9957 1.58
297.60 0.0641 0.9811 0.9753 −0.59 0.9961 1.53
297.60 0.0549 0.9836 0.9799 −0.37 0.9980 1.47
297.60 0.0541 0.9866 0.9803 −0.63 0.9982 1.17
332.60 0.7039 0.8022 0.7254 −9.58 0.7597 −5.30
332.60 0.5107 0.8215 0.8029 −2.26 0.8611 4.82
332.60 0.4970 0.8504 0.8085 −4.93 0.8687 2.15
332.60 0.4562 0.8571 0.8252 −3.72 0.8911 3.97
332.60 0.3759 0.8839 0.8581 −2.92 0.9328 5.54
332.60 0.3614 0.8901 0.8640 −2.93 0.9397 5.57
332.60 0.2886 0.9088 0.8934 −1.69 0.9686 6.58
332.60 0.2853 0.9133 0.8947 −2.03 0.9697 6.17
332.60 0.2429 0.9276 0.9115 −1.74 0.9811 5.77
332.60 0.1993 0.9451 0.9283 −1.77 0.9889 4.64
332.60 0.1562 0.9641 0.9447 −2.01 0.9937 3.07
332.60 0.1212 0.9767 0.9580 −1.91 0.9963 2.01
332.60 0.1170 0.9768 0.9596 −1.76 0.9966 2.02
332.60 0.0808 0.9893 0.9737 −1.58 0.9984 0.92
332.60 0.0796 0.9897 0.9741 −1.57 0.9984 0.88
332.60 0.0454 0.9980 0.9877 −1.04 0.9995 0.15
AAD% 2.27 2.23

poor. The predicted trend from the two correlations as the
mole fraction of TEG approaches unity will be very different
from what this set of experimental data would suggest. Fig. 2
also indicates that Eq. (2) was fitted preferentially to the data
at 297.6 K while the fit to the data at 332.6 K is significantly
poorer. The TST EoS is less accurate at 297.6 K, but is more
accurate at the higher temperature of 332.6 K.
Another important observation can be made from Fig. 2.
The TST EoS predicts slightly lower activity coefficients
than the experimental data at higher temperature. On the
other hand, Parrish’s model predicts higher activity coeffi-
cients at higher temperature. This difference in the predicted
trend can have significant consequences in the extrapolation
of activity coefficients to high temperatures. To test the ex-
trapolation capability, both the TST equation of state and
the Parrish model are extrapolated to 204 ◦ C (477.15 K). The
ability to extrapolate the model to high temperatures to pre-
dict accurate activity coefficients is quite important for strip-
ping processes. Ref. [6] reports that at 204 ◦ C (477.15 K)
and 1.2 atm (121.59 kPa), experience shows approximately
1.2 wt.% water in the lean glycol. The TST equation of state
predicts 1.2 wt.% of water in the lean glycol at 477.15 K un-
der pressure of 123.91 kPa, which is very close to the ob-
served 121.59 kPa, a deviation of only 1.91%. This result
corresponds to a water activity coefficient of approximately
0.7960 at 204 ◦ C. At the same temperature of 204 ◦ C, the
Parrish model gives a value of 0.9477 for the water activity
coefficient. This activity coefficient value will predict a pres-
 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221 219

sure well over the expected value of 121.59 kPa. The TST (30) and (31) as discussed above. Rewrite Eq. (32) as
EoS provides a clear advantage to the use of Eq. (2) because
fw0L (Td ) = Pφw
0L
(Td ) = fwV (Td ) = yw Pφw
V
(Td ) (33)
it can (1) accurately correlate the infinite dilution activity co-
efficients data over a wide temperature range, (2) correlate or
finite concentration activity coefficients data with reasonable
φw
0L (T )
d
accuracy and (3) extrapolate well to higher temperatures. yw = (34)
φw
V (T )
d

where yw is the vapor mole fraction of water (without TEG)

4. Prediction of water dew point and water content
VLE data for TEG–water system commonly are repre-
sented as charts of water dew point lines as a function of con-
tactor temperature and liquid TEG concentrations [3]. The
water dew point is the dew point of the gas, Td , which would
be obtained if the gas were brought to equilibrium with the
TEG solution at the contactor temperature, T. In this work,
the TST equation of state is used to predict the water dew
point and the water content of the TEG–water system as an
alternative to using the water dew point charts [3].
At phase equilibrium, the fugacities of TEG and water in
the liquid and vapor phases are the same:
fTEG
L
= fTEG
V
(30)
fwL = fwV (31)
where fi is the fugacity of component i in the solution. The
fugacity of component i is calculated from the TST equa-
tion of state presented in this work. Assuming that the liquid
compositions and the system temperature, T, are known, Eqs.
(30) and (31) can be used to determine the equilibrium pres-
sure P and vapor-phase compositions. In the context of gas
dehydration, the equilibrium temperature T is referred to as
the contact temperature (temperature of the top tray of the
contactor). The vapor mixture at the contact temperature is at
its dew point. However, the specification for the equilibrium
vapor in gas dehydration is normally in term of its water dew
point (Td ), i.e. the temperature at which pure liquid water
may condense out of the gas phase. One can view this tem-
perature as a hypothetical temperature. In order to compute
Td , TEG is excluded from the gas phase during the dew point
temperature calculation. Since it is assumed that the first drop
of liquid condensed from the vapor at the water dew point is
pure water, we have
fw0L (Td ) = fwV (Td ) (32)
where fw0L (Td ) is the liquid fugacity of pure water at the
water dew point temperature Td and equilibrium pressure P
and fwV (Td ) the vapor fugacity of water in the mixture without
TEG at the dew point temperature Td , equilibrium pressure
P and equilibrium vapor-phase compositions yi . Note that
when the dew point temperature is below the triple point of
water, 273.16 K, the condensed phase is either solid ice or
subcooled water. Following the work of Parrish et al. [2],
subcooled water was used as the standard state fugacity in
this work. The equilibrium P and yi are solved from Eqs.
in equilibrium with the TEG solution at equilibrium temper-
ature (contact temperature) T. The vapor and liquid fugacity
coefficients of water are calculated using the TST equation
of state at Td and at the equilibrium pressure P. Since TEG
is removed from the gas mixture when the water dew point
is performed, the vapor mole fraction of water is normalized
to give yw = 1.0 in this case. Eq. (34) is used to solve for the
water dew point temperature Td . After that, the liquid fugac-
ity of pure water at Td , fw0L (Td ), can then be calculated from
the equation of state.
When the value of fw0L (Td ) at the water dew point temper-
ature Td is obtained, the water content in lbH2 O /MMSCF at
standard condition of T0 = 60 ◦ F (288.71 K) and the equilib-
rium pressure P can be calculated from the following equa-
tion:
n P
= (35)
V Z0 RT0
where Z0 is the gas compressibility factor at T0 and P, and
n the number of moles in vapor volume V. The number of
moles of water, nw , in the vapor then becomes
nw P
= yw (36)
V Z0 RT0
where yw is the mole fraction of water in the gas phase without
TEG. Rewrite Eq. (36) using Eq. (33) and assuming that the
vapor fugacity coefficient of water is 1.0,
nw yw P fwV
= ≈ (37)
V Z0 RT0 Z0 RT0
Substituting Eq. (32) into Eq. (37), we obtain
nw fw0L
= (38)
V Z0 RT0
Given T0 = 60 ◦ F (288.71 K), the gas constant R and assuming
Z0 = 1.0, we obtain the water content in lbH2 O /MMSCF in
terms of fw0L (Td ) at the water dew point temperature Td ,
Water content in lbH2 O /MMSCF = 222 72.23fw0L (Td ) (39)
The water content in SI units is expressed in kg/106 scm:
Water content in kg/106 scm = 356 765.00fw0L (Td ) (40)
where fw0L (Td ) is in the pressure unit of kPa. Since the water
content of lbH2 O /MMSCF is commonly used in the US and
in the field, this unit is used in Table 6.
The typical application range is shown in Tables 5 and 6.
Table 5 shows the prediction of the water dew point temper-
atures of vapor in equilibrium with TEG solutions from the
220 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221

Table 5
Prediction of the water dew point temperature of vapor containing TEG and water in equilibrium with TEG solutions from TST equation of state and prediction
from GPSA recommended model
99.97 wt.% TEG
Contact temperature (K)
277.59 288.71 299.82 310.93 322.04 333.15 344.26
Water dew points of vapor (K)
GPSA 208.15 214.26 220.37 225.93 232.04 237.59 243.15
TST 208.86 214.99 221.00 226.91 232.74 238.52 244.30
99.50 wt.% TEG
Contact temperature (K)
277.59 288.71 299.82 310.93 322.04 333.15 344.26
Water dew points of vapor (K)
GPSA 232.04 239.82 247.59 255.93 263.15 270.93 278.71
TST 232.66 240.47 248.16 255.75 263.22 270.58 277.84

tact temperature at various TEG concentrations ranging from

95.00 to 99.99 wt.% TEG. The result from the TST equation
is quite interesting because it illustrates that the water dew
point is a linear function of the contact temperature at a con-
stant wt.% of TEG. This plot is similar to those presented
in Refs. [2,3] and is useful for practical use in estimating
the water dew point without actually solving the equation of
state.

5. Conclusions

The TST cubic equation of state has been developed suc-

Fig. 3. Equilibrium water dew point vs. contact temperature at various TEG
concentrations in wt.%.
TST equation of state. The water dew points from GPSA are
also included for comparison. Both GPSA and TST equation
of state predict very similar water dew point temperatures,
generally within 1 K.
Table 6 shows the equilibrium water content in
lbH2 O /MMSCF gas in equilibrium with 99.50 wt.% TEG.
The results predicted from the TST equation of state are com-
pared with the reported data [13,14], which cover the range
of temperature from 222 to 277 K. The predicted water con-
tent from the equation of state model agrees with the reported
data very closely over the entire range of temperature. The
calculated equilibrium pressure is also included in Table 6.
Fig. 3 presents the water dew point predicted from the TST
equation of state developed in this work as a function of con-
cessfully to represent the TEG–water binary, which is an in-
dustrial important system for modeling TEG gas dehydration.
This work is an improvement over the empirical hyperbolic
equation of Parrish et al. We also present a methodology for
using the TST equation of state to calculate water dew point
and water content in natural gas systems. The infinite-dilution
and finite-concentration activity coefficients of water in TEG,
water dew point temperatures and water content over the en-
tire application range of temperature, pressure and composi-
tion encountered in a typical TEG dehydration unit predicted
from the TST equation of state match the reported data very
closely.
List of symbols
a, b cubic equation of state parameters
A Helmholtz energy
Aij , Aji , Bij , Bji NRTL binary interaction parameters

Table 6
Prediction of the equilibrium water content in lbH2 O /MMSCF from TST equation of state in equilibrium with 99.50 wt.% TEG
T dew (K) Reported by Predicted from TST equation of state

McKetta and Wehe [13] Bukacek [14] Water content Pressure (Pa)
277.59 390 396 393 838.0
266.48 170 176 174 370.0
255.37 70 72 71 151.0
244.26 28 27 26 56.1
233.15 9.2 9.1 9 18.7
222.04 2.4 2.8 2.6 6.0
 C.H. Twu et al. / Fluid Phase Equilibria 228–229 (2005) 213–221 221

Cr defined in Eq. (20) L liquid phase

C1 defined in Eq. (19) V vapor phase
G Gibbs energy
kij binary interaction parameter
L, M, N parameters in the Twu’s α function References
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