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