Nonequilibrium (NEQ) modeling of three-phase (vapor-liquid-liquid) distillation in a packed column is still lacking of reliable correlations to calculate the interphase rate-based mass transfer. In this paper, extensions of the two most-used correlations [i.e., the Rocha correlation (Rocha, J.A.-, Bravo, J.L.; Fair, J. R. Distillation Columns Containing Structured Packings: A Comprehensive Model for Their Performance. 2. Mass-Transfer Model. Ind. Eng. Client. Res. 1996, 35, 1660) and the Billet and Schultes correlation (Billet, R.; Schultes, A Prediction of Mass Transfer Columns with Dumped and Arranged Packings: Updated Summary of the Calculation Method of Billet & Schultes. Chem. Eng. Res. Des. 1999, 77, 498)] are proposed for mass transfer calculation of three-phase distillation in a packed Column. Parameters used in the correlations are estimated on the basis of comprehensive experimental investigations on both two-phase (vapor-liquid) and three-phase distillation. The experimental database contains 150 different experiments of the 1-butanol/water/1-propanol system for different packings (Montz-Pak B1-350, Raschig Super-Ring 0.3, Rombopak 9M). The parameter estimation with multiple data sets and multipacking turns,out to be a large-scale optimization problem subjected to a large number of nonlinear model equations, To reduce the problem dimension and remove coupling among the parameters, a hierarchical estimation strategy is proposed. The parameters are classified into packing-related and flow-related parameters, which are estimated using two-phase and three-phase distillation experimental data, respectively. In this way, the extension of mass transfer calculation for three-phase distillation is derived. Substantial improvements in the NEQ model prediction have been achieved. Compared with two-phase distillation, an increase of overall mass transfer ability is observed for the studied three-phase system. The extension of the mass transfer calculation can give a reasonable explanation for this observation, providing a better understanding of the intrinsic transfer phenomena inside three-phase packed columns.