In this contribution, integration of bifurcation and steady state analysis into simulation-based hazard and operability study - HAZOP is presented. In this study, advanced mathematical modeling techniques provide valuable support to testing of processes design and process control on different HAZOP deviations. Raw process design together with basic process control is presented as the first layer of protection within general Layer of protection analysis (LOPA). Protection layers are tested by a set of dynamic simulations on different failures. The concept is able to identify hazardous regimes caused by parameter disturbances themselves and also those when inappropriate control loop actions act synergic with already present disturbances. Thus, validation of the applied process control is provided. In this work, CSTR propylene glycol production under Proportional-Integral-Derivative (PID) actions was chosen to identify potential hazard and operability problems of a real chemical process.