Modeling of phase equilibria with CPA using the homomorph approach

Abstract

For association models, like CPA and SAFT, a classical approach is often used for estimating pure-compound and mixture parameters. According to this approach, the pure-compound parameters are estimated from vapor pressure and liquid density data. Then, the binary interaction parameters, kij, are estimated from binary systems; one binary interaction parameter per system. No additional mixing rules are needed for cross-associating systems, but combining rules are required, e.g. the Elliott rule or the so-called CR-1 rule. There is a very large class of mixtures, e.g. water or glycols with aromatic hydrocarbons, chloroform–acetone, esters–water, CO2–water, etc., which are classified as “solvating” or “induced associating”. The classical approach cannot be used and the cross-association interactions are difficult to be estimated a priori since usually no appropriate experimental data exist, while the aforementioned combining rules cannot capture the physical meaning of such interactions (as at least one of the compounds is non-self-associating). Consequently, very often one or more of the interaction parameters are optimized to experimental mixture data. For example, in the case of the CPA EoS, two interaction parameters are often used for solvating systems; one for the physical part (kij) and one for the association part (βcross). This limits the predictive capabilities and possibilities of generalization of the model. In this work we present an approach to reduce the number of adjustable parameters in CPA for solvating systems. The so-called homomorph approach will be used, according to which the kij parameter can be obtained from a corresponding system (homomorph) which has similar physical interactions as the solvating system studied. This leaves only one adjustable parameter for solvating mixtures, the cross-association volume (βcross). It is shown that the homomorph approach can be used with success for mixtures of water and glycols with aromatic hydrocarbons as well as for mixtures of acid gases (CO2, H2S) with alcohols and water. The homomorph approach is less satisfactory for mixtures with fluorocarbons as well as for aqueous mixtures with ethers and esters. In these cases, CPA can correlate liquid–liquid equilibria for solvating systems using two adjustable parameters. The capabilities and limitations of the homomorph approach are discussed.