Fluid Phase Equilibria 248 (2006) 217218

Short communication

Initialization of vaporliquid equilibrium constants for non-hydrocarbon liquid phases

Claude F. Leibovici
H elioparc, 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 sulde rich phases). 2006 Elsevier B.V. All rights reserved.
Keywords: Equilibrium constants; Non-hydrocarbon phases; Flash calculations

1. Introduction When performing ash calculations on hydrocarbon systems at given temperature (T) and pressure (P), the initial values of the equilibrium constants for vapororganic liquid are usually generated using Raoults law: yi Ki = = xi P Pisat (1)

For example, in the case of a water rich phase, initial values such as Ki = Ki = yi P sat = i , wi P yi = 106 , wi i = water i = all other components

are typically used. 2. Proposed approach When very crude estimates are used for the initial equilibrium constants between the vapor phase and a non-hydrocarbon phase, ash calculation may involve some preliminary substitutions steps; in such a case, these specic equilibrium constants have a general tendency of self-correcting rather rapidly. However, if the ash algorithm is based on numerical schemes of higher order (Newton-Raphson, Broyden Powell, etc.), then the calculations can be very severely penalized by such poor estimates. By analogy with what is done using innite dilution activity coefcients in excess Gibbs energy based models, what is proposed here is the following simple procedure: (1) Assume that the non-organic phase is a pure phase. (2) Compute, using the equation of state model, the saturation pressure Psat of the pure component at system temperature.

In practice, most of the time, the vapor pressure equation is generated from Edmisters equation [1]: log10 Pisat 7 1 = (1 + i ) 1 Pci 3 Tri (2)

which leads to the classical so-called Wilsons K-values [3]. The same approach applies with any other method predicting pure component vapor pressure. However, in processes of oil and gas reservoir uids, other liquid phases appear; these are mainly non-hydrocarbon rich phases (the most typical cases being a water rich phase and/or a carbon dioxide rich phase and/or an hydrogen sulde rich phase). For this kind of situations, the problem of the estimation of initial K-values does not seem to have been addressed yet.

Tel.: +33 684 62 89 48; fax: +33 559 84 42 96. E-mail address: c@heliantis.net.

0378-3812/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.uid.2006.08.009

218 Table 1 Example for the 21-component mixture

C.F. Leibovici / Fluid Phase Equilibria 248 (2006) 217218

Logarithms of vaporwater equilibrium constants T = 450 K, P = 3500 kPa Estimation Water Nitrogen Carbon dioxide Hydrogen sulde Methane Ethane Propane n-Butane n-Pentane n-Hexane n-Heptane n-Octane n-Nonane n-Decane n-Undecane n-Dodecane Benzene Toluene o-Xylene m-Xylene p-Xylene 0.133399E +01 0.733250E +01 0.487180E +01 0.368342E +01 0.669479E +01 0.698791E +01 0.719681E +01 0.745239E +01 0.809869E +01 0.927175E +01 0.985284E +01 0.110919E +02 0.122156E +02 0.138521E +02 0.149923E +02 0.170667E +02 0.420295E +01 0.488237E +01 0.482449E +01 0.563692E +01 0.580883E +01 Solution 0.120441E +01 0.721749E +01 0.486480E +01 0.373477E +01 0.663890E +01 0.701696E +01 0.729262E +01 0.761585E +01 0.832520E +01 0.956720E +01 0.102078E +02 0.115089E +02 0.126962E +02 0.143983E +02 0.155978E +02 0.177359E +02 0.450116E +01 0.525041E +01 0.527281E +01 0.607659E +01 0.625128E +01 T = 450 K, P = 7000 kPa Estimation 0.202714E +01 0.663935E +01 0.417865E +01 0.299027E +01 0.600164E +01 0.629477E +01 0.650366E +01 0.675924E +01 0.740554E +01 0.857860E +01 0.915969E +01 0.103988E +02 0.115225E +02 0.131589E +02 0.142992E +02 0.163735E +02 0.350980E +01 0.418923E +01 0.413134E +01 0.494378E +01 0.511569E +01 Solution 0.178515E +01 0.652633E +01 0.425399E +01 0.316003E +01 0.599254E +01 0.643961E +01 0.677344E +01 0.715491E +01 0.791912E +01 0.922044E +01 0.991227E +01 0.112667E +02 0.125102E +02 0.142753E +02 0.155251E +02 0.177199E +02 0.413235E +01 0.493473E +01 0.502710E +01 0.582056E +01 0.600162E +01

(3) At system temperature and computed bubble pressure, compute the innite dilution fugacity coefcients for all components 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 temperature:
0 Ki = L i V i

(3)

(4) Correct for system pressure according to P sat (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 coefcients are immediately accessible for all other components.
0 Ki = Ki

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 sulde, the rst 12 normal parafns, benzene, toluene and the three xylenes. The calculations were done using the process simulator Pro/II for SimSci-Esscor and the selected thermodynamic model is the equation of state proposed by Kabadi and Danner [2].

For the test cases, ash temperature is 450 K. At this temperature, 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 ash 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 coefcients of determination equal signicantly above 0.99). Many other examples have been used for different natures of the third, fourth and fth 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 waterhydrocarbon 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 vaporwater equilibrium constants were always more than acceptable when compared to the converged solutions of the ashes. This speeds up all multiphase ash calculations. References
[1] W.C. Edmister, Compressibility factors and fugacity and equations of state, Petroleum Rener 37 (4) (1958) 173179. [2] V.N. Kabadi, R.P. Danner, A modied SaoveRedlichKwong equation of state for waterhydrocarbon phase equilibria, Ind. Eng. Chem. Proc. Des. Dev. 24 (1985) 537541. [3] G. Wilson, 1968. A modied RedlichKwong EoS, Application to General Physical Data Calculations, Paper No. 15C, Presented at the AIChE 65th National Meeting.