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Vapor-Liquid Equilibria of Water plus

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plus Toluene at 85 kPa

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Article
Vapor#Liquid Equilibria of Water + Triethylene
Glycol (TEG) and Water + TEG + Toluene at 85 kPa
Ali Khosravanipour Mostafazadeh, Mohammad Reza Rahimpour, and Alireza Shariati
J. Chem. Eng. Data, 2009, 54 (3), 876-881• Publication Date (Web): 29 January 2009
Downloaded from http://pubs.acs.org on March 12, 2009

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876 J. Chem. Eng. Data 2009, 54, 876–881

Vapor-Liquid Equilibria of Water + Triethylene Glycol (TEG) and Water +

TEG + Toluene at 85 kPa

Ali Khosravanipour Mostafazadeh, Mohammad Reza Rahimpour,* and Alireza Shariati

School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

In this study, vapor-liquid equilibria data have experimentally been measured for systems water + triethylene
glycol (TEG) and water + TEG + toluene at 85 kPa and various temperatures. The VLE data were determined
in a modified Othmer still, and the samples were analyzed using gas chromatography and titration methods.
The NRTL, UNIQUAC, and Van Laar models were used to correlate the data. The results demonstrate the
enhancement of volatility of water in water + TEG solutions and increasing the purity of the dehydrated
TEG by the addition of toluene. Using this method, the more concentrated TEG can be obtained in the
stripping columns of the natural gas dehydration systems.

Introduction Table 1. Identifications of Materials Used in This Study

chemical purity water F/g · cm-3 supplier
Natural gas dehydration is an important operation in the gas
TEG > 99 % < 0.3 % 1.123 Merck
processing and conditioning industry. In this process, water
toluene > 99 % < 0.01 % 0.866 Merck
vapor is eliminated from natural gas streams for domestic usage distillated water 1.00 Shiraz University
or other downstream gas processes. The level of water vapor
in natural gas should be maintained below a certain value to Table 2. UNIQUAC Parameters for Pure Materials
prevent hydrate formation and minimization of corrosion in parameter TEG toluene water
transportation pipelines.1–3 The standard method for natural gas r 5.59 3.92 0.92
dehydration is by the absorption of water using triethylene q 4.89 2.97 1.40
glycol. The glycols are effective liquid desiccants because of
Table 3. Vapor Pressure Constants for Pure Components27,28a
their high hygroscopic property, low vapor pressure, high boiling
point, and low solubility in natural gas. The four types of glycols comp c1 c2 c3 c4 c5
that have been used for natural gas dehydration are ethylene water 73.649 -7258.2 -7.3037 4.1653e-6 2
glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), toluene 80.877 -6902.4 -8.7761 5.8034e-6 2
TEG 29.36842 -8897.103 -1.467521 2.126367e-6 2
and tetraethylene glycol (T4EG).4 TEG is used in about 95 %
of the glycol dehydration units for natural gas streams. Glycol a
ln Pi ) c1 + c2/T + c3 ln T + c4Tc5 (T in K and p in Pa except for
dehydration units conventionally consist of a contactor and a TEG in kPa).
regenerator. An alternate approach for the enhancement of Table 4. Physical Properties for Pure Components17,25,28,29
reconcentrator performance is the use of stripping agent. In this
approach a volatile hydrocarbon liquid is added to the glycol Tc pc · 10-6 Vc
regeneration system. The hydrocarbon increases the volatility comp M K Pa m3 · kmol-1 zc ω
of water in the solution of water + TEG. Smith and Skiff5 TEG 150.2 769.5 3.320 0.5347 0.2462 1.254
reported that this type of process can achieve compositions of H2O 18.01 647.1 21.94 0.056 0.228 0.343
over 99.99 % with triethylene glycol, resulting in potential dry toluene 92.14 591.8 4.10 0.314 0.262 0.262
gas with the water dew points range in (-73.3 to -95.5) °C.
Toluene and isooctane (2,2,4-trimethyl pentane) are used as water in a water-triethylene glycol solution using an isopiestic
entrainers in the stripping columns of natural gas dehydration method. Gupta et al.10 determined isobaric vapor-liquid
units.6,7 Knowledge of the vapor-liquid equilibrium (VLE) data equilibria for the systems TEG-benzene, toluene-TEG and
is necessary for accurate design and simulation of stripping benzene-N-methylpyrrolidone. Scauzillo11 presented equilib-
columns. Therefore, vapor-liquid equilibria for the systems rium ratios and activity coefficients of water in the systems water
water + TEG and water + TEG + toluene (one of the stripping + TEG + natural gas. Cartaya et al.12 evaluated a local
agents) have been studied in this work. composition model (the LCM model) for the VLE of the binary
mixtures of triethylene glycol in the presence of methane, water,
It is common in industry, such as in extraction and distillation
and benzene. Chung and Luo13 investigated the vapor pressures
units, to add a third component or extract an agent to alter
of the aqueous desiccants. Wise et al.14 determined saturated
relative volatilities in the interest of facilitating extraction or
vapor densities and activities of triethylene glycol-water at low
distillation. Morrison et al.8 investigated the salt effect on the
pressures. Dingman and Lebas15 presented dew point data for
VLE of the water + alcohol system using modified Othmer still.
the binary solution water + TEG. Chen et al.16 reported
Herskowitz and Gottlieb9 determined the activity coefficient of
solubility of glycol in water-hydrocarbon systems. Twu et al.17
* To whom correspondence should be addressed. Tel: +987112303071. Fax: developed an advanced equation of state for modeling the TEG
+987116287294. E-mail: [email protected]. + water system for the glycol gas dehydration process.
10.1021/je800675u CCC: $40.75  2009 American Chemical Society
Published on Web 01/29/2009
 Journal of Chemical & Engineering Data, Vol. 54, No. 3, 2009 877

In this work, an experimental procedure was performed to

determine the VLE data for the binary water + TEG and ternary
water + TEG + toluene systems. A modified Othmer still was
used for taking samples. The samples were analyzed by gas
chromatography (GC) and titration methods. This apparatus was
already used by Smith and Bonner,18 Gupta et al.,10 and
Morrison et al.8 The results were used to optimize the interaction
parameters of the NRTL, UNIQUAC, and Van Laar models.

Experimental Section
Materials. The chemicals were purchased from commercial
sources. The nominal purities of the used chemicals are tabulated
in Table 1.
Figure 1. x,y diagram for water (1) in the water (1) + TEG (2) solution at
p ) 85 kPa: 9, this work; s, Van Laar; ---, NRTL; ---, UNIQUAC Apparatus and Procedure. The VLE data were determined
models results. at 85 kPa pressure in a modified Othmer still, which is a
continuous-distillation still that recirculates the vapor phase.8
Table 5. Vapor-Liquid Data for the System Water (1) + TEG (2) The modified Othmer still provides accurate VLE data in a
at p ) 85 kPa
relatively short experimental time. The still comprises a distil-
t/°C x1 x2 y1 y2 lation flask, a reflux condenser, and condensate return. For
148.1 0.117 0.883 0.9829 0.0171 further details, readers are referred to the paper of Morrison et
141.6 0.176 0.824 0.9908 0.0092 al.8 In this research, a sealed glass recirculating still with two
139.4 0.251 0.749 0.9945 0.0055 magnetic homogenizers was used. The still was slightly modified
127.7 0.373 0.627 0.9978 0.0022
117.3 0.543 0.457 0.9992 0.0008 by providing a magnetic stirrer in condensate and liquid sections.
107.0 0.704 0.296 0.9997 0.0003 Also, the vacuum was performed by a vacuum pump before
103.5 0.781 0.219 0.9998 0.0002 any experiments; then, 85 kPa was applied. The temperature
101.8 0.826 0.174 0.9998 0.0002 sensor model was Pt 100, and the digital temperature detector
100.8 0.856 0.144 0.9999 0.0001
99.8 0.877 0.123 0.9999 0.0001
with ( 0.1 K uncertainty was used.
99.2 0.893 0.107 0.9999 0.0001 Sample Analysis. The samples were taken under steady-state
98.4 0.915 0.085 0.9999 0.0001 conditions. Only the vapor (condensate) samples needed to be
144.0 0.140 0.860 0.9780 0.0220 analyzed. This method also possesses the advantage of rapidly
143.1 0.161 0.839 0.9833 0.0167
140.5 0.182 0.818 0.9872 0.0128
producing experimental data and of directly giving liquid
140.1 0.242 0.758 0.9930 0.0070 composition on a single phase. The analysis of samples was
130.8 0.325 0.675 0.9965 0.0035 carried out by GC on a Varian GC. The GC was equipped with
124.8 0.410 0.590 0.9980 0.0020 (2 m · 0.635 cm) in column packed with Propack Q. Helium
was used as a carrier gas. Two different detectors were used to
Table 6. Vapor-Liquid Equilibrium Data for the System TEG (1)
+ Water (2) + Toluene (3) at p ) 85 kPa analyze the amounts of components in this work. A flame
ionization detector (FID) was applied to obtain the composition
t/°C x1 x2 x3 y1 y2 y3
of hydrocarbons, and a thermal conductivity detector (TCD)
127.7 0.6270 0.3730 0.0000 0.0022 0.9978 0.0000 was chosen to detect the water content. The temperatures of
121.8 0.6197 0.3679 0.0124 0.0015 0.8222 0.1763
117.3 0.6046 0.3590 0.0364 0.0011 0.6564 0.3425 the injector and detector were maintained at 300 °C. The column
112.4 0.5889 0.3496 0.0615 0.0008 0.5707 0.4285 temperature was controlled by programming the temperature.
109.9 0.5834 0.3463 0.0703 0.0007 0.5482 0.4511 After 1 min of holding at t ) 100 °C, the column temperature
106.9 0.5733 0.3403 0.0864 0.0006 0.5180 0.4814 was raised to the final temperature of 220 °C at the rate of 5
104.0 0.5634 0.3346 0.1020 0.0005 0.4952 0.5043
100.3 0.5479 0.3254 0.1267 0.0004 0.4680 0.5316
°C · min-1. Heterogeneous samples were allowed to remain still
97.7 0.5193 0.3084 0.1723 0.0003 0.4396 0.5601 for several hours to be sure that two phases were accurately
95.7 0.4490 0.2666 0.2844 0.0002 0.4104 0.5894 obtained; then, each phase was analyzed. The uncertainty of
95.6 0.3954 0.2348 0.3698 0.0002 0.4026 0.5972 the mole fractions was within ( 0.0005. The composition of
139.4 0.7490 0.2510 0.0000 0.0055 0.9945 0.0000 TEG was determined using a titration method. This method
119.9 0.6810 0.2290 0.0900 0.0014 0.4821 0.5165
108.0 0.6308 0.2108 0.1584 0.0008 0.4008 0.5984 contains the acetylation of the hydroxyl group by acetic
100.1 0.5510 0.1990 0.2500 0.0005 0.3673 0.6322 anhydride with perchloric acid.19 Then, the sample was titrated
98.4 0.5095 0.1703 0.3202 0.0004 0.3427 0.6569 by sodium hydroxide. Liquid compositions were calculated
98.1 0.4595 0.1536 0.3869 0.0003 0.3352 0.6645 throughout the experiments by overall material balance similar

Table 7. Binary Interaction Parameters for the System Water (1) + Toluene (2) + TEG (3)
couple of components interaction parameters (UNIQUAC) interaction parameters (NRTL) interaction parameters (Van Laar)
water + TEG
water - TEG a13 ) -2.729 a31 ) 2.112 a13 ) -0.0015 a31 ) -1.704 R13 ) 2.850 a13 ) 1.288 a31 ) 6.828
b13 ) 0.004 b31 ) -0.003 b13 ) -0.234 b31 ) 0.004 b13 ) -526.887 b31 ) -257.520
water + TEG + toluene
water - toluene a12 ) -2.390 a21 ) -3.815 a12 ) 4.374 a21 ) 2.439 R12 ) -0.136 a12 ) -3.272 a21 ) 6.351
b12 ) 0.004 b21 ) 0.006 b12 ) -0.007 b21 ) -0.004 b12 ) 2205.364 b21 ) 239.429
water - TEG a13 ) -3.087 a31 ) 2.304 a13 ) -12.312 a31 ) 0.095 R13 ) -0.889 a13 ) 40.877 a31 ) 3.772
b13 ) 0.005 b31 ) -0.004 b13 ) 0.020 b31 ) -0.0002 b13 ) 131.318 b31 ) -2161.730
toluene - TEG a23 ) 6.537 a32 ) 2.478 a23 ) 1.109 a32 ) 1.359 R23 ) -2.200 a23 ) -7.415 a32 ) -5.910
b23 ) 0.011 b32 ) -0.004 b23 ) -0.002 b32 ) -0.002 b23 ) 2078.915 b32 ) 1955.915
878 Journal of Chemical & Engineering Data, Vol. 54, No. 3, 2009

Figure 2. Comparison of correlations with literature data: ---, Van Laar; ---, NRTL; s, UNIQUAC. (a) Activity coefficient of water in the water + TEG
solution. Experimental data from ref 9: 9, at t ) 24.5 °C; 2, at t ) 59.5 °C. (b) Water dew points. Experimental data from ref 15: 9, at t ) 37.5 °C; 2,
at t ) 60.1 °C.

and Van Laar23 equations. Because the pressure was low and
this investigation was performed at constant pressure, the
virial equation was used to calculate the vapor-phase fugacity
coefficients. The UNIQUAC equation for the activity coef-
ficient of component i in a multicomponent mixture is given
by24

∑ xjlj - qi ln[∑ θjτji] +

φi z θi φi
ln γi ) ln + qi ln + li -
xi 2 φi xi j j
θjτij
qi - qi ∑ (2)
j ∑ θkτkj
k
Figure 3. Activity coefficients of water (1) + TEG (2) in their solution at
p ) 85 kPa correlated by: ---, NRTL; ---, UNIQUAC; s, Van Laar The NRTL equation24 was also applied for the calculation
equations; 9, experimental data in this work.

( )
of activity coefficients of components in the liquid phase

to the work of Morrison et al.8 The method has sufficient ∑ xjτjiGji xjGij
∑ xkτkjGkj
accuracy to determine small traces of glycol. The uncertainty
ln γi )
j
+ ∑ τij -
k
(3)
was ( 0.1 % of TEG.
∑ xkGki j ∑ xkGkj ∑ xkGkj
k k k
Model Development
For the specific case of multicomponent VLE20 where

yipφ̂i Gij ) exp(-Rijτij)

γi ) (1) (4)
xipisatφisat In general, the temperature dependence parameters for NRTL
The liquid-phase activity coefficients of the components and UNIQUAC equations are presented by eqs 5 and 6,
in the mixtures were calculated from UNIQUAC,21 NRTL,22 respectively

Figure 4. Relative volatility of water to TEG (Rw) in the TEG (1) + water (2) solution with the addition of toluene (3) (a) as a function of toluene (3) mole
fraction in liquid phase and (b) as a function of equilibrium temperature correlated by: ---, NRTL; s, UNIQUAC; ---, Van Laar equations; 9, experimental
data in this work.
 Journal of Chemical & Engineering Data, Vol. 54, No. 3, 2009 879

bij In this work, a rigorous method was used for VLE calcula-
τij ) aij + + cij ln T + dijT (5) tions. This method was suggested by Smith et al.20 The
T

( )
UNIQUAC parameters, the vapor pressures, and the physical
bij properties of components are reported in Tables 2, 3, and 4,
τij ) exp aij + + cij ln T + dijT (6)
T respectively.
The logarithmic term is used only if liquid-liquid equi-
libria have to be described and because the two parameters Results and Discussion
usually are used for temperature-dependence binary interac- The experimental VLE data for system water and TEG are
tion parameters; therefore, the following equation is applied presented in Table 5. Also, the experimental vapor-liquid data
in to NRTL and UNIQUAC models, and it was observed for ternary system containing water, TEG, and toluene are given
that the following equation has the most consistency for the in Table 6. From this table, it is clear that the volatility of water
mentioned systems increases in the presence of toluene, and the equilibrium
τij ) aij + bijT (7) temperature declines when toluene is added to the mixture. The
experimental data of the water + TEG and water + TEG +
The simpler model (Van Laar23) was also correlated for the toluene systems were correlated using UNIQUAC, NRTL, and
previously mentioned systems Van Laar equations. The estimation of the binary interactions

[ ( )]
of the aforesaid models was based on the minimization of the
AiBi
ln γi ) Ai(1 - zi)2 1 + 2zi -1 (8) objective function, OF, in terms of the difference between
|AiBi| calculated and experimental logarithmic activity coefficients
where values. The function OF used in this work can be expressed as
n m
|Ai|xi
zi )
|Ai|xi + |Bi|(1 - xi)
(9) OF ) min ∑ ∑ (ln γexptl
ij
- ln γijcalcd)2 (15)
i)1 j)1

Ai ) ∑ xjAij/(1 - xi) (10) where γijexptl and γijcalcd are the experimental and calculated activity
j coefficients of component i, respectively. The subscripts i,j

∑ xjAji/(1 - xi)
denote the component and data, respectively. The binary
Bi ) (11) interaction parameters in UNIQUAC, NRTL, and Van Laar
j
equations between TEG + water, TEG + toluene, and water +
For the Van Laar equation, the interaction parameter is as toluene are listed in Table 7.
follows Figure 1 depicts the y,x diagram of water in the water + TEG
solution at 85 kPa. Because there is a large difference between
bij
Aij ) aij + (12) the boiling points of TEG and water, the amount of TEG in the
T vapor phase is very small. As can be seen from this Figure, the
The fugacity coefficient of component i in a gas mixture is water mole fraction in the vapor phase is greater than 0.98;
calculated by the following equation20 therefore, water is more volatile relative to TEG. The correla-

{ }
tions for this system have very good agreement with experi-
ln φ̂i ) P/RT Bii +
1
2 ∑ ∑ [yiyk(2δji - δjk)] (13) mental data. The correlations have been compared with experi-
mental data from Herskowitz and Gottlieb9 and Dingman and
j k
Lebas.15 Figure 2a shows the consistency of the water activity
The second virial coefficient was calculated from the equation
predicted by correlations with experimental data. Also, Figure
RTcij 0 2b compares the water dew point predicted by correlations and
Bij ) (B + ωijB1) (14) literature data. The experimental and correlated logarithmic
Pcij
activity coefficients by mentioned equations for water and TEG
and B0 and B1 were computed as a function of reduced are shown in Figure 3. Good agreements are observed between
temperature. model results and experimental data.

Figure 5. Activity coefficient of water + TEG + toluene in their solution at p ) 85 kPa (a) as a function of TEG mole fraction and (b) as a function of
toluene: ], TEG (1); 0, water (2); 4, toluene (3). Correlated by: ---, NRTL; s, UNIQUAC; ---, Van Laar equations.
880 Journal of Chemical & Engineering Data, Vol. 54, No. 3, 2009

Table 8. Root-Mean-Square Deviation (RMSD)a The composition of water in the liquid phase decreases in
mixture NRTL UNIQUAC Van Laar the presence of toluene, which is demonstrated in Figure 6. This
water + TEG 0.032 0.016 0.002 Figure shows the T-x-y diagram of the mixtures water + TEG
water + TEG + toluene 0.392 0.635 21.913 and water + TEG + toluene. This Figure shows that by the
addition of toluene, the T-x-y diagram of TEG + water shifts
a
{∑in∑jm{γijexptl - γijcalcd}2/n}0.5.
to lower compositions of water in the liquid phase (on a toluene-
free basis) at the same temperature, which means that by the
addition of toluene, the composition of water in the liquid phase
is less than its composition without toluene. The effects
demonstrate that the toluene is more soluble in the less-volatile
component (TEG) and therefore increases the relative volatility
of water.

Conclusions
In the natural gas dehydration process, knowledge of ther-
modynamic behavior of materials is very important for the basic
design and operation at industry. Isobaric VLE of water-triethylene
glycol (TEG) and the effect of toluene on this solution have
been investigated theoretically and experimentally. The VLE
data were determined in a modified Othmer still, which is the
continuous-distillation still that recirculates the vapor phase, and
Figure 6. T-x-y diagram of water (1) + TEG (2) solution in the presence the samples were analyzed using GC and a titration method.
and in the absence of toluene using model (UNIQUAC) results at The experimental data of the binary (water + TEG) and ternary
atmospheric pressure: s, water (1) + TEG (2); ---, water (1) + TEG
(2) + toluene (3), on a toluene-free basis.
systems (water + TEG + toluene) were tuned using Van Laar,
quasichemical activity coefficient (UNIQUAC), and nonrandom
The relative volatility of water to TEG is two liquid (NRTL) activity coefficients models. Good agree-
ments were obtained for the water + TEG system, but only
yw
⁄xw NRTL and UNIQUAC models are suggested for the ternary
Rw ) y (16) system. The results demonstrate that the volatility of water
TEG
⁄xTEG increases in the water + triethylene glycol solution, and thus
the purity of residual TEG increases by the addition of toluene.
The relative volatility of water to TEG in the ternary system
By the use of this approach, the separation of TEG and water
water + TEG + toluene is shown in Figure 4. Figure 4a shows
is achieved with higher performance in the stripping columns
that the relative volatility of water to TEG increases by the
of the natural gas dehydration units.
addition of toluene. Figure 4b shows that equilibrium temper-
ature declines by the addition of toluene. Moreover, this Figure
Acknowledgment
shows that water volatility increases with decreasing tempera-
ture. The equilibrium temperature decreases when the toluene We thank Dr. Sona Raeissi for her useful suggestions.
mole fraction increases. Both parts of the Figure show that the
Van Laar model has more deviation from experimental data. Literature Cited
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