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Energy Sources, Part A: Recovery,

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A Triethylene Glycol–Water System: A

Study of the TEG Regeneration Processes
in Natural Gas Dehydration Plants
a a a
V. Piemonte , M. Maschietti & F. Gironi
a
Department of Chemical Engineering Materials & Environment ,
University of Roma “Sapienza” , Roma , Italy
Published online: 19 Jan 2012.

To cite this article: V. Piemonte , M. Maschietti & F. Gironi (2012) A Triethylene Glycol–Water System:
A Study of the TEG Regeneration Processes in Natural Gas Dehydration Plants, Energy Sources, Part A:
Recovery, Utilization, and Environmental Effects, 34:5, 456-464, DOI: 10.1080/15567031003627930

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 Energy Sources, Part A, 34:456–464, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567031003627930

A Triethylene Glycol–Water System: A Study of the

TEG Regeneration Processes in Natural Gas
Dehydration Plants

V. PIEMONTE,1 M. MASCHIETTI,1 and F. GIRONI1

1
Department of Chemical Engineering Materials & Environment,
University of Roma “Sapienza”, Roma, Italy
Downloaded by [University of Windsor] at 02:23 17 July 2014

Abstract Natural gas pipeline transportation requires very low water content in the
gas stream in order to avoid condensation or hydrate formation. To reach this goal,
when triethylene glycol is used to dehydrate natural gas, after the absorption step,
triethylene glycol must be regenerated to levels substantially above 98.5–99.0% by
weight available from atmospheric distillation of glycol-water mixtures. In order to
regenerate triethylene glycol to higher purity levels, some of the methods used require
a stripping gas, a solvent, or to perform the distillation under vacuum. Another method
to perform a further dehydration of triethylene glycol is the use of a water exhauster,
known as Coldfinger, where the vapor in equilibrium with the liquid to be dehydrated
is continuously condensed and removed. In the first part of this work, measurements of
boiling temperatures are reported for binary mixtures of triethylene glycol and water
at pressures of 50, 100, 200, and 400 mmHg. The experimental data obtained were
correlated by employing the NRTL model, with temperature-dependent parameters, to
express activities in the liquid phase. The fitted NRTL parameters were then used in the
Hysys process simulator to perform a process simulation of a natural gas dehydration
plant, provided both with a Coldfinger water exhauster and a conventional stripping
column for triethylene glycol regeneration.

Keywords Coldfinger, dehydration, natural gas, triethylene glycol regeneration, strip-

ping gas

1. Introduction
Natural gas at the producing well contains significant quantities of water vapor. Typically,
the gas is water-saturated at the condition of pressure and temperature of the well and a
dehydration process is required. In fact, water content must be reduced in order to prevent
liquid water condensation and hydrate formation in the pipeline transportation system.
Nowadays, typical values of allowable water content in the gas transmission lines range
from 70 to 120 mg/Nm3 (Huffmaster, 2004; Hubbard and Campbell, 2000).
Among methods available for natural gas dehydration, absorption by means of
triethylene glycol (TEG) is one of the most common. Water removal from the gas stream
takes place by means of countercurrent contact between the gas, fed to the bottom of a
contactor tower, and TEG, which is a liquid with a great affinity for water, fed at the top
of it.

Address correspondence to Dr. Vincenzo Piemonte, Department of Chemical Engineering

Materials & Environment, University of Rome, via Eudossiana 18, Rome 00181, Italy. E-mail:
piemonte@ingchim.ing.uniroma1.it

456
 TEG Regeneration Processes 457

The crucial part of the process is represented by TEG regeneration. If the water-rich
TEG is distilled in a simple atmospheric column, TEG can not be regenerated to levels
above 98.8–98.9% by weight. This is caused by the reboiler operating temperature, which
cannot be fixed at temperatures above 204ıC. In fact, this temperature must be regarded
as an upper limit for TEG processing because of thermal degradation at higher values
(Steele et al., 1996).
In the past, these regeneration levels were sufficient because values of allowable
water content in the lean gas were higher and regeneration was commonly performed in
a simple atmospheric still column. On the other hand, in order to reach current water
content specifications, it is necessary to regenerate TEG up to levels substantially above
99.0% by weight.
For these reasons, several alternative regeneration processes (vacuum distillation,
stripping gas, azeotropic distillation, etc.) have been proposed in order to enhance TEG
regeneration levels.
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If TEG–water distillation is performed under vacuum, TEG can be regenerated up to

99.9% by weight (Hubbard and Campbell, 2000). Another possibility is represented by
using some of the dehydrated natural gas as a stripping gas in order to further dehydrate
TEG. The contact with lean TEG exiting the still column can take place in the surge drum
where TEG make-up is introduced or in an appropriate stripping column. Operating in
this way lean TEG purity can be increased above 99.9% by weight, but the consumption
of some of the dehydrated gas represents an economic loss. Furthermore, the use of
stripping gas causes a considerable increase of the gas sent to flare, unless an expensive
recovery system is arranged. Purity of lean TEG exiting the still column can also be
enhanced by using a circulating solvent (such as heptane or octane) to perform an
azeotropic distillation instead of the simple TEG–water distillation. In this way lean TEG
concentration can be increased up to 99.99% by weight but plant complexity and costs
are increased because of the need of a three-phase separator at the top of the distillator,
the needs of treatments for the oily water discharged from this separator, and devices
for the solvent circulation line (such as a circulation pump and a heater) (Hubbard and
Campbell, 2000).
If the required purity of the lean TEG is in the range 99.0–99.9% by weight, the
Coldfinger process (Reid, 1971, 1978) could be a valuable alternative. This process is
similar to the conventional dehydration process, except for the use of an apparatus, also
called water exhauster, where the liquid stream exiting the reboiler of the still column is
further dehydrated. The Coldfinger process could be advantageous because no stripping
gas, solvent, or further energy consumption are required and because of the simplicity of
the water exhauster, which can be easily installed as an addition to a conventional plant.
In the first part of this work, measurements of boiling temperatures are reported for
binary mixtures of TEG and water at various pressures. Then experimental data obtained
were correlated by employing the NRTL model, with temperature-dependent parameters,
to express activities in the liquid phase. The fitted NRTL parameters were then used in
the Hysys process simulator to perform a process simulation of a natural gas dehydration
plant, provided both with a Coldfinger water exhauster and a conventional stripping
column for TEG regeneration.
Due to the lack of literature data on the performance of natural gas dehydration
plants provided with Coldfinger apparatus, our Hysys simulations cannot be validated
against any plant process data. Therefore, the conclusions drawn in this work about the
Coldfinger plant reliability must be taken only as a first raw analysis finalized to highlight
the potentialities of the Coldfinger system.
 458 V. Piemonte et al.

2. Experimental Section
Triethylene glycol has been purchased from Fluka Chemical Co. and has a minimum
guaranteed purity of 99% by weight and a water content less than 0.08%. Bidistilled
and deionized water has been purchased from Carlo Erba and shows a conductivity less
than 1 S cm 1 at room temperature. Both products have been used without further
purification.
The experimental runs have been carried out by means of a vapor recirculation
already used in previous works. Details on the experimental apparatus are reported
elsewhere (Gironi et al., 1981). Temperatures are measured by means of a resistance
thermometer with an accuracy of ˙0.1 K. Prior to performing the experimental runs,
the thermometer has been calibrated by measuring the solid-liquid and the vapor-liquid
equilibrium temperature of pure water at atmospheric pressure.
Vacuum is maintained by a mechanical pump connected to the vapor condenser
of the ebulliometer and is controlled by a Cartesian manostat that makes possible the
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regulation of the total pressure within 1 mmHg. The absolute pressure is measured by
reading the saturation temperature of pure water that boils in an ebulliometer connected
in parallel with the ebulliometer containing the solution to be measured. Each solution is
prepared gravimetrically with an accuracy equal to ˙0.01 mg; the accuracy of the mole
fraction data has been estimated better than ˙0.0001.
The boiling temperature of liquid mixtures of TEG (1) and water (2) that have been
measured in this work at pressures of 50, 100, 200, and 400 mmHg are reported in
Table 1. The obtained results show a remarkable variation of the boiling temperature
with liquid phase composition in the TEG-rich zone.
The correlation of the experimental data has been initially performed by means of a
'-' method based on the Peng Robinson (PR) equation of state (EOS).
The PR-EOS has provided unsatisfactory results in the correlation of the boiling
temperature data, both with Van der Waals and Wong-Sandler mixing rules. The Twu-

Table 1
Experimental and calculated boiling temperature data at 50, 100, 200, and 400 mmHg
Boiling temperature, K

x1 Pexp D 50 Pcal c D 50 Pexp D 100 Pcal c D 100 Pexp D 200 Pcal c D 200 Pexp D 400 Pcal c D 400

0.200 317.25 318.09 330.85 332.14 346.05 347.70 363.35 365.02

0.399 325.15 326.21 340.65 342.08 356.55 359.59 374.25 378.37
0.604 337.75 340.20 355.15 357.89 372.75 376.51 397.45 397.52
0.695 345.15 351.20 363.75 369.31 386.45 390.01 407.85 412.55
0.795 356.25 369.33 381.65 389.63 403.35 412.43 428.65 438.16
0.812 359.65 373.51 385.75 394.57 409.75 417.79 434.05 444.16
0.824 364.45 377.50 390.25 398.37 413.75 421.99 446.05 448.01
0.836 366.25 380.47 397.45 401.94 418.35 425.09 450.05 453.11
0.855 371.75 387.38 405.35 409.48 423.85 434.17 456.35 461.78
0.874 377.55 395.44 417.35 418.17 435.25 443.45 467.85 471.52
0.887 387.15 400.12 430.05 423.27 444.35 448.45 480.65 477.51
0.901 394.35 408.16 438.65 431.17 458.45 456.90 487.45 483.19
0.922 405.25 420.54 446.35 446.60 471.15 470.47 498.85 485.61
0.944 428.95 430.86 472.45 457.89 482.45 479.90 511.65 508.39
0.960 446.65 443.32 480.45 466.01 498.65 490.57 518.85 516.90
0.976 461.65 458.21 484.85 479.49 503.85 502.58 521.55 527.44
1 471.65 471.74 489.75 491.47 508.15 512.93 534.15 536.44
ARD% 2.31 ARD% 1.34 ARD% 1.18 ARD% 1.01
 TEG Regeneration Processes 459

Sim-Tassone (TST)-EOS has not been employed because it is expected to provide similar
results, when compared to the PR-EOS, according to the findings of previous work on
this subject (Gironi et al., 2010; Herskowitz and Gottlieb, 1984; Parrish et al., 1986;
Twu et al., 2005). Therefore, in this case, the -' approach has been preferred, choosing
an activity coefficient model for the calculation of fugacities in the liquid phase and the
PR-EOS for the calculation of fugacities in the vapor phase. In particular, the equilibrium
conditions have been calculated by means of Eq. (1), where the hypothesis of Lewis-
Randall has been assumed:

yi
P
'io .P; T / D xi
i
psi .T /
'io .psi ; T /
'Li .P; T; psi /; (1)

where xi and yi are the equilibrium mole fractions of i-component in the liquid and
vapor phases, respectively; T and P are the boiling temperature and the total pressure,
respectively; and 'io stands for the fugacity coefficient of the pure component i as a
vapor, whereas 'Li represents the Poynting correction. The vapor pressure .psi / and the
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molar liquid volume of water have been obtained from Perry and Green (1998), whereas
the vapor pressure and the molar liquid volume of TEG have been evaluated by means
of the Wagner equation and from the experimental data reported in Steele et al. (2002).
In Eq. (1), the activity coefficients have been expressed by means of the NRTL model
by assuming a fixed value of the non randomness parameter ˛12 , whereas the interac-
tion parameters 12 and 21 have been assumed as fitting parameters. The temperature
dependence of 12 and 12 has been assumed as follows:

b12
12 D a12 C ; (2)
RT
b21
21 D a21 C : (3)
RT
In the correlation of the experimental data, the values of the four unknown parame-
ters .a12 ; a21 ; b12; b21 / have been obtained by minimization of the following objective
function:
X
m X
n
ˆD Œ.Pkl /exp .Pkl /cal c 2 ; (4)
kD1 l D1

where m is equal to 4 because the experimental data have been obtained at 4 different
pressure values and l is equal to 17 because at each pressure 17 different liquid mixtures
have been investigated.
In Table 1, the values of the parameters are reported by means of the NRTL equation
and the vapor-liquid equilibria have been evaluated at each pressure. The calculated values
of the initial boiling temperatures are compared to the experimental ones in Table 1. The
agreement between experimental and calculated values appears to be satisfactory at each
pressure: the average relative deviation (ARD) ranges from 1.01% at 400 mmHg to 2.31%
at 50 mmHg.

3. Gas Dehydration Process

A typical flow scheme of the natural gas dehydration process, with TEG regeneration
enhanced by the Coldfinger apparatus, is reported in Figure 1.
 460 V. Piemonte et al.
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Figure 1. Typical flow scheme of natural gas dehydration with the Coldfinger regeneration process.

Wet gas is fed to the bottom of the absorption column (A), whereas regenerated
TEG (13) is fed to the top of it. As a consequence of the contact between gas and TEG,
a stream of dry gas is obtained from the top, whereas a stream of water-rich TEG (1) is
withdrawn from the bottom of the column and is conveyed to the regeneration section.
Since the absorption column operates at high pressure (typically 40–80 bar) and low
temperature (typically 20–60ıC), whereas the regeneration section operates at pressure
around 1 bar and a high temperature (up to 204ıC), water-rich TEG is expanded and
heated before entering the still column (S). In order to heat water-rich TEG, heat can be
conveniently recovered from the regeneration section. In particular, water-rich TEG after
expansion (2) can be pre-heated while removing heat at the Coldfinger tubes and then
(3) at the condenser of the still column.
Because of heating and reducing pressure, some flash gas is produced and separated
from the liquid stream in a flash drum (D). After filtration (F) to remove impurities,
water-rich TEG undergoes another pre-heating step in a heat-exchanger (H), recovering
heat from lean regenerated TEG (11), and then is fed to the still column.
Water-rich TEG is distilled in the still column. The reboiler (R) can be heated by
exhaust gases of the combustion of a small fraction of natural gas produced in the unit
and used as a fuel. The reboiler temperature must be limited at 204ı C to avoid TEG
thermal degradation. In this condition, TEG mass fraction at the reboiler will be around
98.8–98.9% by weight.
In order to increase TEG mass fraction, this liquid stream is conveyed to the
Coldfinger apparatus (C), which can be realized in a separate vessel or in a vessel
integrated with the reboiler itself, as in the case of Figure 1. Heat removal at the condenser
placed in the upper part of the Coldfinger apparatus can be conveniently provided by
water-rich TEG as explained above.
As an alternative, if a greater amount of heat removal is required in order to reach
higher regeneration levels, cooling water can be employed to give a lower temperature of
 TEG Regeneration Processes 461

the cold tubes. Condensed liquid on the “cold fingers” is reintroduced inside the column.
Because of the small quantity of this liquid stream, its inlet point has a negligible effect
and so it can be conveniently reintroduced inside the reboiler. Regenerated TEG exiting
the Coldfinger apparatus is cooled (H) as far as possible before being pumped (P) back
to the absorption column.

4. Process Simulation
The process represented in Figure 1 was studied by means of the process simulator Hysys.
Phase equilibria conditions were represented by means of a thermodynamic model based
on the NRTL equations. Correct representation of phase equilibria conditions of the
binary system TEG–water, especially at high temperature and for mixture composition
close to water infinite dilution, proved to be an essential requirement for regeneration
process design. The thermodynamic study on the TEG–water system was carried out on
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the experimental data as reported above; therefore, to represent the binary TEG–water
system, a simulator data bank was not used.
Since commercial process simulators do not provide Coldfinger apparatus by default,
a user-defined external routine (Coldfinger routine) was generated in order to include the
water exhauster in the whole process scheme. A first raw analysis of the performance
of the natural gas dehydration with Coldfinger regeneration process was carried out on a
case study. A comparison between the Coldfinger process and the regeneration process
by stripping gas was also carried out.
The NRTL parameters used in this study for the binary system TEG-water are
reported in Table 2, while a typical wet gas composition was selected as reported in
Table 3. Other process parameters were fixed as follows:
 Total inlet gas flow rate: 100,000 kg/h
 Absorption column pressure: 50 bar
 Absorption column theoretical stages: 4
 Still column theoretical stages: 3
 Still column reflux ratio: 0.10
The number of theoretical stages of the absorption column was not increased above the
reported value because this parameter has a poor effect on gas dehydration, especially
when compared with regenerated TEG purity, which is the key factor of the process.
Similarly, the number of theoretical stages at the still column was kept at the reported
low value because no further effect on TEG dehydration can be achieved by increasing
this parameter. The still column reflux ratio was fixed at the minimal value, which

Table 2
Values of the NRTL parameters

Parameter TEG (1)–H2O (2)

˛12 0.3
a12 1.076
b12 , joule/mol 311.28
a21 1.623
b21 , joule/mol 379.11
 462 V. Piemonte et al.

Table 3
Natural (wet) gas composition

Component Weight fraction

Methane 0.3853
Ethane 0.2408
Propane 0.1948
n-Butane 0.0687
iso-Butane 0.0325
C5 and superior 0.0592
Water 0.0044
Nitrogen 0.0122
Carbon dioxide 0.0021
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allowed TEG losses to be reduced around zero (0.001% by weight on the circulating
glycol). As for the absorption column, TEG losses were less than 0.1% by weight in all
simulations.
The process was studied for different wet gas temperatures (from 20 to 60ı C), varying
the liquid to gas ratio (L/G) at the absorber column in the range of 0.03–0.13, which is
to say that circulating TEG was varied from 3,000 to 13,000 kg/h. Heat removal at the
Coldfinger was realized exchanging with TEG from the absorption column, which is the
more convenient solution. Continuous lines in Figure 2 show the results obtained by these
simulations. As expected, process performance is strongly influenced by the temperature
of the wet gas entering the absorption column. In fact, the temperature profile of the

Figure 2. Water content in the lean gas as a function of the liquid to feed ratio in the absorption
column referred to four different wet gas temperatures. Continuous lines refer to Coldfinger
regeneration process. Dashed lines refer to regeneration by means of stripping gas.
 TEG Regeneration Processes 463

absorption column depends primarily on the wet gas temperature because of the low
(L/G) ratio. Furthermore, at a higher wet gas temperature, the ratio (L/G) has a greater
influence on the dehydration level that is possible to obtain.
In the case study under consideration, the use of the Coldfinger apparatus allows to
reach typical water content specifications for wet gas temperatures up to 50ı C. At lower
gas temperatures, the process is more efficient for two reasons: favorable thermodynamic
conditions at the absorption column and improvement of Coldfinger regeneration because
of the lower temperature of water-rich TEG, which can provide a larger heat removal
rate at the “cold fingers.” However, even at 60ı C it is possible to strongly reduce water
content in the dehydrated gas stream, down to approximately 200 mg/Nm3 . In this case,
a further improvement can be obtained refrigerating the Coldfinger with cold water from
an external circuit, in order to reach higher levels of regenerated TEG purity.
A classical dehydration process scheme, with TEG regeneration enhanced by using
some of the dehydrated gas, was simulated in order to provide a comparison with the
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Coldfinger process. The process flow scheme is the same as Figure 1, except for the
absence of the Coldfinger, which is substituted by a stripping column fed by some gas
split from the dehydrated gas stream.
The number of theoretical stages of the stripping column was fixed at 2, which is
a typical value for this process. All the other process parameters were kept equal to the
values reported above.
In a preliminary set of simulations, stripping gas flow rate was varied until similar
water content specifications, with respect to Coldfinger process, were obtained. This
similarity was found operating the stripping column with a gas flow rate equal to 100
kg/h.
The dependence of water content on liquid to gas ratio for this process is represented
by the dashed lines shown in Figure 2.
Operating the stripping column at a constant gas flow rate, a minimum water content
was found at high liquid to gas ratio. This is caused by two contrasting effects: increasing
the circulating liquid improves the dehydration at the absorption column but regeneration
becomes more difficult. This behavior does not appear with the Coldfinger process
because, when circulating TEG increases, the heat removal rate at the “cold fingers”
increases as well. A correct design of the Coldfinger can lead to a constant regeneration
level while circulating liquid increases.
From this first raw analysis, the Coldifnger process seems to be reliable; it could
be view as a possible alternative to the conventional process with stripping gas mainly
from the gas consumption point of view; in fact, the gas consumption of the regeneration
process with stripping gas resulted to be from 2.5 to 6 times greater than the Coldfinger
process.

5. Conclusions
The experimental boiling temperatures of TEG–water mixtures have been measured at
pressures equal to 50, 100, 200, and 400 mmHg. The experimental data have been corre-
lated employing the NRTL model for the activities in the liquid phase. The values of the
NRTL binary parameters have been calculated from the correlation of our experimental
data and were used to carry out a first raw analysis of the performance of the natural
gas dehydration, including both Coldfinger and a stripping gas regeneration process. The
plant simulation was carried out by the Hysys process simulator.
 464 V. Piemonte et al.

The raw analysis of the Coldfinger apparatus carried out in this work can be viewed as
a preliminary step to evaluate the reliability of this new process for the TEG regeneration;
furthermore, experimental data on the Coldfinger process are indispensable to confirm
the findings of our process simulations. To this end, a pilot plant (laboratory scale) of
the Coldfinger apparatus is now under construction.

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