Chemical productions operated in extreme conditions (high pressure, high temperature) require a detailed analysis of all potentially dangerous situations that can lead to a major industrial accident and thus cause a loss of life and property. Many accidents in the near or distant history underline the need of a detailed safety analysis in process industries, not only in the phase of plant design but also during the operation of the plant. It would be shown that simulation of a chemical unit using an appropriate mathematical model and the nonlinear analysis theory can be a suitable tool for safety analysis. This approach is based on mathematical modeling of a process unit where both the steady-state analysis, including the analysis of the steady states multiplicity and stability, and the dynamic simulation are used. Principal objective of this paper is to summarize problems regarding the model-based hazard identification in processes. A case study, focused on phenomena of multiple steady states in ammonia synthesis reactor will be presented. The influence of the model complexity and model parameters uncertainly on the quality of safety analysis would be underline. (C) 2014 Elsevier Ltd. All rights reserved.