Fluid Phase Equilibria 248 (2006) 217–218

Short communication

Initialization of vapor–liquid equilibrium constants for

non-hydrocarbon liquid phases
Claude F. Leibovici ∗
Hélioparc, 2, Avenue Pierre Angot, 64053 Pau Cedex, France
Received 6 June 2006; received in revised form 4 August 2006; accepted 6 August 2006
Available online 14 August 2006

Abstract
A simple method is proposed for an a priori estimation of equilibrium constants between vapor and non-hydrocarbon phases which are very rich
with regard to one component (case of water, carbon dioxide, hydrogen sulfide rich phases).
© 2006 Elsevier B.V. All rights reserved.

Keywords: Equilibrium constants; Non-hydrocarbon phases; Flash calculations

1. Introduction For example, in the case of a water rich phase, initial values
such as
When performing flash calculations on hydrocarbon systems
yi P sat
at given temperature (T) and pressure (P), the initial values of Ki = = i , i = water
the equilibrium constants for vapor–organic liquid are usually wi P
generated using Raoult’s law:
yi
Ki = = 106 , i = all other components
yi Pisat wi
Ki = = (1)
xi P are typically used.

In practice, most of the time, the vapor pressure equation is

2. Proposed approach
generated from Edmister’s equation [1]:

   When very crude estimates are used for the initial equilib-
Pisat 7 1
log10 = (1 + ωi ) 1 − (2) rium constants between the vapor phase and a non-hydrocarbon
Pci 3 Tri phase, flash calculation may involve some preliminary substitu-
tions steps; in such a case, these specific equilibrium constants
which leads to the classical so-called Wilson’s K-values [3]. The
have a general tendency of self-correcting rather rapidly. How-
same approach applies with any other method predicting pure
ever, if the flash algorithm is based on numerical schemes of
component vapor pressure.
higher order (Newton-Raphson, Broyden Powell, etc.), then the
However, in processes of oil and gas reservoir fluids, other
calculations can be very severely penalized by such poor esti-
liquid phases appear; these are mainly non-hydrocarbon rich
mates.
phases (the most typical cases being a water rich phase and/or a
By analogy with what is done using infinite dilution activ-
carbon dioxide rich phase and/or an hydrogen sulfide rich phase).
ity coefficients in excess Gibbs energy based models, what is
For this kind of situations, the problem of the estimation of initial
proposed here is the following simple procedure:
K-values does not seem to have been addressed yet.

(1) Assume that the non-organic phase is a pure phase.

∗ Tel.: +33 684 62 89 48; fax: +33 559 84 42 96.
(2) Compute, using the equation of state model, the saturation
E-mail address: cfl@heliantis.net. pressure Psat of the pure component at system temperature.

0378-3812/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.08.009
218 C.F. Leibovici / Fluid Phase Equilibria 248 (2006) 217–218

Table 1
Example for the 21-component mixture
Logarithms of vapor–water equilibrium constants

T = 450 K, P = 3500 kPa T = 450 K, P = 7000 kPa

Estimation Solution Estimation Solution

Water −0.133399E +01 −0.120441E +01 −0.202714E +01 −0.178515E +01

Nitrogen 0.733250E +01 0.721749E +01 0.663935E +01 0.652633E +01
Carbon dioxide 0.487180E +01 0.486480E +01 0.417865E +01 0.425399E +01
Hydrogen sulfide 0.368342E +01 0.373477E +01 0.299027E +01 0.316003E +01
Methane 0.669479E +01 0.663890E +01 0.600164E +01 0.599254E +01
Ethane 0.698791E +01 0.701696E +01 0.629477E +01 0.643961E +01
Propane 0.719681E +01 0.729262E +01 0.650366E +01 0.677344E +01
n-Butane 0.745239E +01 0.761585E +01 0.675924E +01 0.715491E +01
n-Pentane 0.809869E +01 0.832520E +01 0.740554E +01 0.791912E +01
n-Hexane 0.927175E +01 0.956720E +01 0.857860E +01 0.922044E +01
n-Heptane 0.985284E +01 0.102078E +02 0.915969E +01 0.991227E +01
n-Octane 0.110919E +02 0.115089E +02 0.103988E +02 0.112667E +02
n-Nonane 0.122156E +02 0.126962E +02 0.115225E +02 0.125102E +02
n-Decane 0.138521E +02 0.143983E +02 0.131589E +02 0.142753E +02
n-Undecane 0.149923E +02 0.155978E +02 0.142992E +02 0.155251E +02
n-Dodecane 0.170667E +02 0.177359E +02 0.163735E +02 0.177199E +02
Benzene 0.420295E +01 0.450116E +01 0.350980E +01 0.413235E +01
Toluene 0.488237E +01 0.525041E +01 0.418923E +01 0.493473E +01
o-Xylene 0.482449E +01 0.527281E +01 0.413134E +01 0.502710E +01
m-Xylene 0.563692E +01 0.607659E +01 0.494378E +01 0.582056E +01
p-Xylene 0.580883E +01 0.625128E +01 0.511569E +01 0.600162E +01

(3) At system temperature and computed bubble pressure, com-
pute the infinite dilution fugacity coefficients for all compo-
nents in both vapor and liquid phases (these numbers always
exist even if some of them could be extremely small). Then,
compute for the saturation pressure and system tempera-
ture:
ϕiL
Ki0 =
ϕiV
(4) Correct for system pressure according to
P sat
Ki = Ki0 (4)
P
This procedure involves very simple calculations since, once
vapor and liquid compressibility factors have been obtained for
the pure component at its saturation conditions, the fugacity
coefficients are immediately accessible for all other compo-
nents.
3. Test example
In order to illustrate the simple approach described above, we
considered a system containing 20 mol of water plus 1 mol of
each of the 20 following components: nitrogen, carbon dioxide,
hydrogen sulfide, the first 12 normal paraffin’s, benzene, toluene
and the three xylenes. The calculations were done using the
process simulator Pro/II for SimSci-Esscor and the selected ther-
modynamic model is the equation of state proposed by Kabadi
and Danner [2].
For the test cases, flash temperature is 450 K. At this tem-
perature, the equation of state predicts for pure water a vapor
pressure equal to 922 kPa. Table 1 summarizes the logarithms
of predicted initial K-values as well as the rigorous solution for
the flash performed on the overall system at pressures equal to
3500 and 7000 kPa (both cases result in three-phase split). The
agreement is good (least-square analysis shows coefficients of
(3) determination equal significantly above 0.99).
Many other examples have been used for different natures of
the third, fourth and fifth possible phases; all of them led to the
same quality of results. However, as one could intuitively expect,
these estimates are better when the phase is less contaminated
by the other components but, in any case, they are always more
than acceptable.
For water–hydrocarbon systems, many calculations have
been performed in particular at low temperatures and even
below the ice point of water. The estimates so provided for
the vapor–water equilibrium constants were always more than
acceptable when compared to the converged solutions of the
flashes. This speeds up all multiphase flash calculations.
References
[1] W.C. Edmister, Compressibility factors and fugacity and equations of state,
Petroleum Refiner 37 (4) (1958) 173–179.
[2] V.N. Kabadi, R.P. Danner, A modified Saove–Redlich–Kwong equation of
state for water–hydrocarbon phase equilibria, Ind. Eng. Chem. Proc. Des.
Dev. 24 (1985) 537–541.
[3] G. Wilson, 1968. A modified Redlich–Kwong EoS, Application to General
Physical Data Calculations, Paper No. 15C, Presented at the AIChE 65th
National Meeting.