This paper addresses the study of a pyro-gasification plant designed, built, and operated to recover inert metals from different types of solid waste. Experimental tests were carried out using pulper as the solid waste. However, while a reliable composition analysis of the produced syngas was carried out, a precise composition evaluation of the pulper used during the experimental activities was not performed and the related data were characterized by unacceptable uncertainty. Therefore, with the aim of reliably characterizing the plant operation, a thermochemical model of the gasification process was setup to simulate the equilibrium operation of the plant and a vector optimization methodology was used to calibrate the numerical model. Then, a decision-making problem was solved to identify the most suitable optimal solution between those belonging to the Pareto optimal front, thus obtaining reliable composition data for the adopted pulper waste. In particular, four different identification criteria were applied for the selection of small subset of solutions over the 3138 dominant solutions found. Among them, the solution (i.e., set of calibration parameters) that minimizes the experimental-numerical difference between the lower heating value of the produced syngas seemed to provide the most reliable approximation of the real plant operation. Finally, a possible plant configuration is proposed for the energetic valorization of the pulper waste and its overall conversion process efficiency is estimated.