Wax phase equilibria: developing a thermodynamic model using a systematic approach

Abstract

Reservoir hydrocarbon fluids contain heavy paraffins that may form solid phases of wax at low temperatures. Problems associated with wax formation and deposition are a major concern in production and transportation of hydrocarbon fluids. The industry has directed considerable efforts towards generating reliable experimental data and developing thermodynamic models for estimating the wax phase boundary. The cloud point temperature, i.e. the wax appearance temperature (WAT) is commonly measured in laboratories and traditionally used in developing and/or validating wax models. However, the WAT is not necessarily an equilibrium point, and its value can depend on experimental procedures. Furthermore, when determining the wax phase boundary at pipeline conditions, the common practice is to measure the wax phase boundary at atmospheric pressure, then apply the results to real pipeline pressure conditions. However, neglecting the effect of pressure and associated fluid thermophysical/compositional changes can lead to unreliable results. In this paper, a new thermodynamic model for wax is proposed and validated against wax disappearance temperature (WDT) data for a number of binary and multi-component systems. The required thermodynamic properties of pure n-paraffins are first estimated, and then a new approach for describing wax solids, based on the UNIQUAC equation, is described. Finally, the impact of pressure on wax phase equilibria is addressed. The newly developed model demonstrates good reliability for describing solids behaviour in hydrocarbon systems. Furthermore, the model is capable of predicting the amount of wax precipitated and its composition. The predictions compare well with independent experimental data, demonstrating the reliability of the thermodynamic approach.