Optimization of the production planning is crucial for the economic success of a petroleum refinery. Nevertheless, it is a difficult task, because of the large scale of the system and the complexity of the processes involved. Part 1 of this series of two papers addresses the formulation of process models for petroleum refinery planning. First, a generic formulation of nonlinear refinery planning model is adopted from the literature. Subsequently, the formulation of nonlinear empirical models for crude distillation units (CDUs) and a fluid catalytic cracking (FCC) unit is addressed. These empirical models were successfully validated using rigorous process simulators. Finally, the results from model validation showed that the accuracy of model predictions is as good as the current empirical process models reported in the literature, while the empirical process models proposed in this work overcome the limitations of both linear and nonlinear empirical models for CDUs and FCC units previously developed by other authors. Part 2 [Ind. Eng. Chem. Res. 2011, DOT: 10.1021/ie200304v] involves the implementation of nonlinear empirical process models in the petroleum refinery planning.