Fluid Phase Equilibria 202 (2002) 399412

Thermodynamic properties of synthetic natural gases Part 4. Dew point curves of synthetic natural gases and their mixtures with water: measurement and correlation
Departamento de Innovacin Tecnolgica, Enags S.A., Zaragoza, Spain Departamento de Qumica Orgnica y Qumica Fsica, Facultad de Ciencias, Universidad de Zaragoza, 50009 Zaragoza, Spain c Laboratoire de Chimie Physique de Marseille, Facult des Sciences de Luminy, Universit de la Mditerrane, 13288 Marseille Cedex 9, France
b

Susana Avila a, Sofa T. Blanco b, Inmaculada Velasco b, Evelyne Rauzy c, Santos Otn b,
a

Received 8 February 2002; received in revised form 22 May 2002; accepted 22 May 2002

Abstract
Experimental measurements of dew points for ve synthetic natural gases (SNG) + water mixtures were carried out between 2.1 105 and 73.2 105 Pa in the temperature range from 224.3 to 270.2 K. The experimental results were analysed in terms of both an equation of state (EOS) model and an excess functionEOS method, which reproduced the experimental data with an AAD from 2.1 to 3.4 K and from 1.9 to 3.0 K, respectively. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Dew point; Experimental method; Equation of state; Excess function

1. Introduction
Knowledge of the experimental water dew point in natural gases is important in the design of dehydration units to prevent the undesired formation of ice or hydrates and for the corrosion of the pipes or blockages during transport. In order to understand the inuence of water on the vapourliquid equilibrium of natural gases, ve synthetic natural gas (SNG)+ water mixtures were studied. The compositions of the SNGs used in this work are the same as those of the natural gases supplied in Spain as liqueed natural gases (LNG). A water dew point generation experimental apparatus was built and commissioned [1] and the dew point curves of the four dry SNG used in this work and their mixtures with water and methanol were
E-mail address: santos@posta.unizar.es (S. Otn).

Corresponding author. Tel.: +34-976-761-199; fax: +34-976-761-202.

0378-3812/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S0378-3812(02)00166-8

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obtained [2]. The results on ve SNG + water mixtures at pressures from 2.1 105 to 73.2 105 Pa and temperatures from 224.3 to 270.2 K are presented here. The experimental results obtained on the multi-component systems were analysed in terms of both an equation of state (EOS) model and an excess functionEOS method, which reproduced the experimental data within an AAD from 2.1 to 3.4 K and from 1.9 to 3.0 K, respectively.

2. Experimental
The experimental dew point ranges from 2.1 105 to 73.2 105 Pa at temperatures from 224.3 to 270.2 K. The four SNGs used in this work were prepared according to the gravimetric method (International Standard ISO 6142:1982) [3], by Air Liquide and AbellLinde. The compositions of these SNGs and their accuracy specied by the supplier are listed in Table 1. The experimental method used for this work is based on the generation of saturated gases with water by condensation of this compound in two successive temperature-controlled condensers with continuous gas ow at specied pressures. The dew point generation apparatus used for our experimental data collecting was described in a previous paper [1]. After controlled expansion, the gas is saturated with water vapour by owing through liquid water in an isolated saturator held at laboratory temperature. The temperature of water condensation is then achieved in two successive stainless steel condensers. The rst condenser temperature is set to a value lying between ambient and the temperature of the second condenser. In doing so, the quantity of liquid collected into the second condenser is minimised. The concentration of water in the gas is measured at the outlet of the dew point generation system, using a Karl Fischer titration, according to the standard method [4] at atmospheric pressure. By doing so, the water content reference value of the gaseous phase is obtained. The dew point values of SNG + water mixtures are measured by means of a chilled mirror instrument [5]. The chilled mirror instrument input pressure is set using a regulator valve. When the apparatus reaches a stable value of dew temperature, both pressure and temperature are recorded. In this way, the values of the temperature and pressure of the dew point curve of the mixture generated are obtained. The instrumentation, implemented to analyse the content of water and to carry out the dew point measurements, is the following:
Table 1 Composition of synthetic natural gases (mol%) and absolute or relative accuracy specied by the supplier Component Nitrogen Methane Ethane Propane i-Butane n-Butane i-Pentane n-Pentane n-Hexane Gas 1 0.67 0.02 89.96 0.23 8.22 0.17 0.90 0.02 0.11 0.01 0.13 0.01 0.0084 0.0002 0.0032 0.001 Gas 2 0.48 0.01 88.76 0.24 8.54 0.17 1.68 0.04 0.22 0.01 0.29 0.01 0.0182 0.0004 0.0084 0.0002 Gas 3 0.862 2% 86.484 0.2% 9.832 1% 2.388 1% 0.183 2% 0.231 2% 0.0139 2% 0.0063 2% Gas 4 0.410 0.04 96.465 0.10 2.510 0.05 0.213 0.005 0.184 0.004 0.197 0.004 0.0096 0.0002 0.0100 0.0002 0.0010 0.0001

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Mitsubishi CA 06 Karl Fischer Titrator, coupled with an Elster wet gas meter Type Gr. 00, E51, 0.2% accuracy. MBW Dew Point Instrument, Mod. DP3-D-HP-K2. The cooling of the mirror is achieved by cascaded Peltier elements and the dew point mirror temperature is opto-electronically controlled. Pressure transmitter. With a maximum error of 0.1% in the calibrated range from 0 to 100 105 Pa. Prior to the study of SNG + water dew points, the performance of both analytical methods and experimental procedures was checked. The uncertainty of the water dew point measurement, given by the supplier of the MBW Dew Point Instrument was 0.3 K for dew point temperatures from 198.2 to 228.2 K and 0.2 K for dew point temperature between 228.2 and 273.2 K. To obtain the precision of the analysis of water content, repeated analysis of the water content of a standard nitrogen + water mixture prepared by Air Liquide was carried out. The measured values were equal to the standard water content within a rejecting percentage of 0.05 [6]. The absolute average deviation was of 0.5 106 kg m3 (STP)1 for a mean value of the water content of 59.0 106 kg m3 (STP). In order to evaluate the precision of the water dew point, both generation and determination, repeated generation of methane + water mixtures were carried out, and the water content and the dew point curve were measured. The results obtained in the performance evaluation are the following: for the water content, the absolute average deviation was 1.0 106 kg m3 (STP) for a mean water content of 19.6 106 kg m3 (STP); for the dew point pressure, the relative average deviation was 3% in a range from 2.1 105 to 71.1 105 Pa; for the dew point temperature, the absolute average deviation was 0.4 K in a range from 225.8 to 259.1 K. Reference conditions for the volume are 273.15 K and 1.01325 105 Pa. The test was achieved on a water dew point of 72 105 Pa and 258.1 K in pure methane.

3. Results
The water content in the vapour phase and the dew point curves of the SNG + water mixtures generated with the moisture-generation system were determined and the results of the experiments are collected in Table 2.

4. Theory
4.1. Introduction

Equations of state, such as the SantisBreedveldPrausnitz EOS [7], the NakamuraBreedveld Prausnitz EOS [8], the PengRobinson EOS [9] and the RobinsonPengNg EOS [10] yield good results in calculation of water dew point of natural gases at higher temperatures than the temperature of the natural gas pipeline network. In this work, a model based on a modied PengRobinson EOS [11] is used in order to obtain a good description of water vapour pressure of ice and liquid water. This equation allows predicting properly, the water dew point curve in the usual temperature and pressure range of importance for natural gas pipelines.
1

STP: standard temperature and pressure (273.15 K, 1.01325 105 Pa).

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Table 2 Experimental dew points temperatures and pressures for (SNG + water) mixtures
T (K)

P (105 Pa)

Gas 1; water = 16.8 106 kg m3 (STP) 225.8 233.3 239.8 243.6 246.4 249.5 251.3 252.6 253.7 254.7 255.6 256.3 257.1 257.8 258.5 Gas 2; water = 48.3 106 kg m3 (STP) 237.0 244.3 250.1 254.4 257.5 259.7 261.5 263.0 264.4 265.6 266.8 267.5 268.7 269.5 270.2 Gas 3; water = 26.1 106 kg m3 (STP) 228.7 238.3 244.4 248.8 251.8 253.5 255.7 256.8 258.4 259.7 260.7 261.7 262.4

2.3 5.0 10.1 15.2 19.9 25.0 30.4 35.0 39.8 45.0 50.5 54.1 60.1 65.7 73.2 2.6 5.7 10.0 15.1 20.1 25.1 29.9 34.9 39.5 44.8 49.9 54.0 60.6 66.2 71.8 2.3 5.7 10.1 15.5 19.9 25.7 29.8 35.3 39.8 45.3 49.6 55.6 60.0

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Table 2 (Continued ) T (K) 263.1 263.8 Gas 3; water = 48.5 106 kg m3 (STP) 231.1 241.9 249.6 255.3 257.0 259.4 261.4 263.0 264.1 265.3 266.4 267.4 268.3 269.2 270.1 Gas 4; water = 15.6 106 kg m3 (STP) 224.3 233.3 240.5 244.8 247.2 249.5 251.5 252.8 253.9 255.1 256.0 256.8 257.5 257.9 258.7

P (105 Pa)

65.3 70.0 2.2 5.3 9.7 16.3 20.4 25.2 30.5 35.3 39.6 44.7 49.9 54.6 60.0 65.8 71.6 2.1 5.3 10.0 15.2 20.1 25.0 30.6 34.9 40.1 45.0 49.8 54.6 58.5 63.1 68.4

On the other hand, classical models, such as UNIFAC [12], DISQUAC [13] or modied UNIFAC [14] allow the prediction of the vapourliquid equilibrium at low pressure for systems which contain a polar component but these models are not suited for high pressure calculations. In this work, an excess functionEOS method developed by Pneloux et al. [15] founded on the zeroth order approximation of Guggenheims model is used. For the EOS based models, binary data are required to calculate the interaction parameters. In the excess functionEOS models, these parameters can be calculated using a group contribution method. This makes possible to predict dew point curves of real natural gases. For this is important because not always binary experimental data for all the components of the so-called C6+ fraction exist.

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This work is part of a research which aims to study the inuence of the presence of methanol, as an additive of natural gas, in the water dew point of natural gases [2,16]. The excess functionEOS method used in this work has been chosen because it allows to be modied to have into account the self-association of methanol in the mixtures. In order to evaluate these two models for the prediction of water, dew points of multi-component systems in the studied temperature and pressure ranges, a comparison between the experimental and calculated values was carried out. The values of dew temperature of the vapour phase for the studied systems are calculated by means of both methods using the experimental values of pressure and composition obtained in the present work.
4.2. Description of the EOS model

The EOS model used in this work is based on a modied PengRobinson EOS [11] in order to obtain a good description of water vapour pressure both on ice and liquid water. The binary interaction parameters between the natural gas components and water were also obtained. The EOS used is the PengRobinson cubic EOS [9] of the form:
P =

with and

a 2 v b v + 2bv b2

RT

(1) (2) (3) (4) (5)

b(T ) = b(Tc ) a(T ) = a(Tc )(Tr , )

where and

1/2 = 1 + (1 Tr1/2 ) = 0.374640 + 1.54226 0.269922

In case of water, the following equation is used [11]: 1/2 = A0 + A1 (1 Tr1/2 ) + A2 (1 Tr1/2 )2 + A3 (1 Tr1/2 )4 (6) Different values for the coefcients A0 A3 are used for T < 273.15 K and T > 273.15 K (Table 3). For the calculation of parameter a and b in case of mixtures, classical mixing rules are used of the form [11]:
n

a=

i=1

xi xj aij

(7) (8)

and
aij = ai aj (1 kij )

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Table 3 Values of the coefcients A0 , A1 , A2 and A3 used in the EOS model [11] Coefcient
A0 A1 A2 A3
n

223.15 K T < 273.15 K 0.77404 1.58484 0 2.28241

273.15 K T 313.15 K 1 0.90544 0.21378 0.26

b=

xi bi
i=1

(9) (10)

with and

kij = kji kii = kjj = 0

(11) Due to the use of a changed function for water, new binary interaction parameters for natural gas components and water were obtained [11]. In case of CO2 + H2 O, CH4 + H2 O and C2 H6 + H2 O, the following temperature function for kij is used:
kij (T ) = kij,0 + kij,1

Values for the binary interaction parameters kij ,0 and kij ,1 used in this work are given in Tables 4 and 5.
4.3. Description of the excess functionEOS method

T 1 273.15

(12)

In order to represent the vapourliquid equilibria of the mixtures studied, a model founded on the zeroth approximation of Guggenheims reticular model was selected. The model satises two important conditions:
Table 4 Values of the temperature independent part of the binary interaction parameters, kij ,0 used in Eq. (12) for the EOS model [11] N2 N2 H2 O CH4 C2 H6 C3 H8 i-C4 H10 n-C4 H10 i-C5 H12 n-C5 H12 n-C6 H14 0 0.4800 0.0311 0.0515 0.0852 0.1033 0.0800 0.0922 0.1000 0.1496 H2 O 0 0.6510 0.6350 0.5300 0.6900 0.6900 0.5000 0.5000 0.5000 CH4 0 C2 H6 C3 H 8
i-C4 H10 n-C4 H10 i-C5 H12 n-C5 H12 n-C6 H14

0.0026

0.0140 0.0256 0.0133 0.0056 0.0230 0.0422

0 0.0011 0.0067 0.0096 0.0160 0.0078 0.0100

0.0078

0.0033 0.0111 0.0267 0.0007

0.0004

0 0.0174 0.0056

0 0.0600

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Table 5 Values of the temperature dependent part of the binary interaction parameters, kij ,1 , used in Eq. (12) for the EOS model [11] N2 N2 H2 O CH4 C2 H 6 C 3 H8 i-C4 H10 n-C4 H10 i-C5 H12 n-C5 H12 n-C6 H14 0 0 0 0 0 0 0 0 0 0 H2 O
1.3850 0.9300

CH4 0 0 0 0 0 0 0 0

C2 H 6

C3 H8

i-C4 H10

n-C4 H10

i-C5 H12

n-C5 H12

n-C6 H14

0 0 0 0 0 0

0 0 0 0 0 0 0

0 0 0 0 0 0

0 0 0 0 0

0 0 0 0

0 0 0

0 0

(1) The Helmholtz energies of the pure components are calculated by an EOS. (2) The excess functions are obtained at constant packing fraction, . This means that the value of the packing fraction, for each component in the mixture is the corresponding value of the pure component. This assumption leads to:
= b bi = , v vi i = 1, . . . , p

(13)

The molar Helmholtz energy of a mixture, A may be written as follows:

A = Aid RT ln(1 ) xi ai Q() + AE res bi i=1
p

(14)

where Aid is the ideal mixture molar Helmholtz energy, ai the attractive parameter of component i of a translated PengRobinson cubic EOS [17,18], bi the co-volume of component, AE the residual excess res Helmholtz energy and Q() is expressed as follows:
Q() = Q () d 0 1 +

(15) (16) (17)

where
Q () =

and

is written by means of a formalism that enables to separate the composition and packing fraction variables: AE = E(T , x)Q() (18) res
AE res

= 2( 2 + 1)

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For the rst term on the right hand side of Eq. (18), the following equations are used [19]:
E(T , x) =

2qm

p i=1

with
Kij =

qi xi

p j =1

qj xj Kij +

p i=1

qi xi

p j =1

1/3 1/3 qj xj Lji

(19)

2 1 Eij + Eij

and

(20) (21) (22) (23)

2 1 Lij = Eij Eij

Lij = Lji
p

qm =

qk xk
k=1

and (24) where the subscripts i and j refer to the components i and j of the mixture with p components, qi is the molecular surface of the component i. It is assumed that (qi /qj ) = (bi /bj ) where is an adjustable parameter. Kij and Lij are two binary interaction parameters between components i and j, which are 1 2 calculated from Eqs. (20) and (21). The interchange energies, Eij and Eij , are calculated using a group contribution method as follows [19]:
qk = k bk

1 1 Eij =

2 k=1 l=1
N N

(ik jk )(il jl )A1 (T ) kl (ik jk )(il jl )A2 (T ) kl

with with

1 0 Akl = 1 Akl 2 0 Akl = 2 Akl

T0 T T0 T

0 1 Bkl

(25) (26)

1 2 Eij =

0 2 Bkl

2 k=1 l=1

0 0 0 where 1 Akl , 1 Bkl , 2 A0 and 2 Bkl are group interaction parameters. kl

5. Comparison with experiment and discussion

The experimental dew point data and the dew points calculated with both the EOS model and the excess functionEOS method are represented in Figs. 14. The experimental dew point curves of dry SNG mixtures obtained in another work [2] are also represented in Figs. 14 in order to better explain the inuence of the presence of water in the dew point curves of natural gases which contain water. As it can be seen in Figs. 14, an increase of water content of the SNG + water mixtures leads to a displacement of their dew point curves to higher values of temperatures and pressures. For the systems studied, the water dew point value seems to be independent on the composition of SNGs used.

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Fig. 1. Experimental hydrocarbon dew point curve of Gas 1 ( ) and comparison between experimental dew points curves (symbol) and calculated with the EOS model (dotted line) and with the excess functionEOS method (line) for the system: ( ) Gas 1 + 16.8 106 kg m3 (STP) water.

In the studied mixtures, after comparing the hydrocarbon dew point curves of SNGs, which have low potential of risk of condensation, with the water dew point curves of SNG + water systems, it can be concluded that the presence of water amounts from 15.6 to 48.5 106 kg m3 (STP) increases considerably the risk of condensation of mixtures in the whole range of pressure studied. After comparing the experimental and calculated dew point curves in Figs. 14, it can be concluded that both theoretical methods used in this work reproduce quite satisfactorily the experimental dew point data within the AAD for dew point temperatures between 2.1 and 3.4 K with the EOS model and from

Fig. 2. Experimental hydrocarbon dew point curve of Gas 2 ( ) and comparison between experimental dew points curves (symbol) and calculated with the EOS model (dotted line) and with the excess functionEOS method (line) for the system: ( ) Gas 2 + 48.3 106 kg m3 (STP) water.

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409

Fig. 3. Experimental hydrocarbon dew point curve of Gas 3 ( ) and comparison between experimental dew points curves (symbol) and calculated with the EOS model (dotted line) and with the excess functionEOS method (line) for the system: ( ) Gas 3 + 26.1 106 kg m3 (STP) water; ( ), Gas 3 + 48.5 106 kg m3 (STP) water.

1.9 to 3.0 K with excess functionEOS method. Values of the AAD obtained for each dew point curve are presented in Table 6. It should be noted that in the EOS model an inuence of the water content on AAD values is observed. The greatest deviations occur for the mixtures with the lowest water contents. This can be due to the experimental error in the water content analysis at very low water contents. No inuence of pressure and temperature is found for the values of the AAD for both theoretical models.

Fig. 4. Experimental hydrocarbon dew point curve of Gas 4 ( ) and comparison between experimental dew points curves (symbol) and calculated with the EOS model (dotted line) and with the excess functionEOS method (line) for the system: ( ) Gas 4 + 15.6 106 kg m3 (STP) water.

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Table 6 Values of AAD1 (EOS model) and AAD2 (excess functionEOS method) and experimental ranges of dew temperatures and pressures for mixtures (SNG + water) SNG mixture Gas 1 Gas 2 Gas 3 Gas 3 Gas 4 16.8 48.3 26.1 48.5 15.6
water

(106 kg m3 (STP))

T range (K)

P range (105 Pa)

AAD1 (K)

AAD2 (K)

225.8258.5 237.0270.2 228.7263.8 231.1270.1 224.3258.7

2.373.2 2.671.8 2.370.0 2.271.6 2.168.4

2.2 2.5 2.7 2.1 3.4

1.9 3.0 3.0 2.9 1.9

From the results obtained in this work and in the previous work [20] it can be concluded that the introduction of a group contribution method, as is used in case of excess functionEOS method, does not impair predictions with respect to the EOS method with interaction parameters obtained from binary experimental data, for SNG, with or without CO2 , and water systems. It makes the excess functionEOS method very useful to predict the water dew point of real natural gases, provided that, not always binary experimental data for all components of the so-called C6 + fraction exist. A
List of symbols a EOS energy parameter (Pa m6 mol2 )

A Akl b

k K, L N N p P q Q Q R T T0
v

1 2 Eij , Eij

coefcient used in the EOS model molar Helmholtz energy (J mol1 ) group interaction parameter between groups k and l (J m3 ) co-volume; EOS size parameter (m3 mol1 ) terms of the interchange energy (J m3 ) binary interaction parameter in EOS model binary interaction parameters (J m3 ) in excess functionEOS model in the excess functionEOS model, number of groups in a solution for calculating AAD, number of dew points which constitute a dew point curve number of components in the mixture pressure (Pa) molecular surface (m2 ) integral of Q / between 0 and a packing fraction function gas constant (8.314 J mol1 K1 ) temperature (K) reference temperature (298.15 K) molar volume (m3 mol1 ) function of the acentric factor and the reduced temperature surface area fraction of group k in molecule i adjustable parameter, proportionality coefcient between the surface measure, q and the co-volume, v

Greek symbols
ik

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411

water

constant of the translated PengRobinson cubic EOS packing fraction function of the acentric factor experimental mean value of water content (106 kg m3 (STP)) acentric factor critical value referring to components i, j referring to groups k, l referring to a point of a dew point curve in the calculation of AAD reduced value residual

c i, j k, l
n

Subscripts

r res

Superscripts

cal exp E id

calculated experimental excess property ideal solution property

Acknowledgements
The authors acknowledge nancial and technical support from Enags S.A. during the experimental part of this work.

Appendix A
For comparison between the calculated and experimental dew point temperatures for each studied dew point curve, we used the deviation AAD = 1
N
N i=1

Tnexp Tncal

where N is the number of dew points that constitute a dew point curve.

References
[1] S.T. Blanco, I. Velasco, E. Rauzy, S. Otn, Fluid Phase Equilib. 161 (1999) 107117. [2] S. Avila, S.T. Blanco, I. Velasco, E. Rauzy, S. Otn, Energy and Fuels 4 (2002), in press. [3] ISO 6142, Analyse des gazPrparation des mlanges de gaz pour talonnage, Mthodes pondrales, International Organization of Standardization, Geneva, Switzerland, 1981. [4] ISO 10101, Natural gas-determination of water by the KarlFischer method, International Organization of Standardization, Geneva, Switzerland, 1993.

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[5] ISO 6327, Gas analysis. Determination of the water dew point of natural gas. Cooled surface condensation hygrometers, International Organization of Standardization, Geneva, Switzerland, 1981. [6] ISO 2854, Statistical interpretation of datatechniques of estimation and tests relating to means and variances, International Organization of Standardization, Geneva, Switzerland, 1976. [7] R. de Santis, G.J.F. Breedveld, J.M. Prausnitz, Ind. Chem. Process Des. Dev. 13 (1974) 374. [8] R. Nakamura, G.J.F. Breedveld, J.M. Prausnitz, Ind. Eng. Chem. Process Des. Dev. 15 (1976) 557. [9] D.Y. Peng, D.B. Robinson, Can. J. Chem. Eng. 54 (1976) 595599. [10] D.B. Robinson, D.Y. Peng, H. Ng, Hydrocarbon Process 58 (9) (1979) 269. [11] K. Althaus, Messung und Berechung von Wassergehalten kohlenwasserstoffhaltiger Gasgemische. Doktors der Ingenieurwissenschaften (Dr.-Ing.), Fakultt fr Chemieingnieurwesen der Universitt Fridereciana zu Karlsruhe (Technische Hochschule) genehmigte, Germany, 1999. [12] D.S. Abrams, J.M. Prausnitz, AIChE J. 21 (1975) 116128. [13] H.V. Kehiaian, Fluid Phase Equilib. 13 (1983) 243252. [14] B.L. Larsen, P. Rasmussen, A. Fredenslund, Ind. Eng. Chem. Res. 26 (1987) 22742286. [15] A. Pneloux, W. Abdoul, E. Rauzy, Fluid Phase Equilib. 47 (1989) 115132. [16] S. Avila, S.T. Blanco, I. Velasco, E. Rauzy, S. Otn, in: Proceedings of the 2001 International Gas Research Conference (IGRC), 2001, p. TP-17. [17] A. Pneloux, E. Rauzy, R. Frze, Fluid Phase Equilib. 8 (1982) 723. [18] E. Rauzy, Les mthodes simples de calcul des quilibres liquidevapeur sous pression, Thse dEtat-Sciences, Universit AixMarseille II, France, 1982. [19] H. Hocq, Etude exprimentale et modlisation thermodynamique des mlanges mthanol-eau-hydrocarbures. Thse en Sciences, Universit de Droit, dEconomie et des Sciences dAixMarseille III, France, 1994. [20] S. Avila, S.T. Blanco, I. Velasco, E. Rauzy, S. Otn, Energy and Fuels, in press.