Comparing with continuous production process, unsteady operation process, such as startup and shutdown,tends to abnormal situations due to a large number of operations of operators and dynamic state changes involved. To guarantee a safe operation, process hazard analysis(PHA) is very important to proactively identify the potential safety problems. In the chemical process industry, hazard and operability(HAZOP) analysis is the most widely used method. In this paper, based on proposed qualitative simulation and inference method, an automatic HAZOP analysis method for unsteady operation processes is proposed. Mass transfer and relationships among process variables are expressed by Petri net–directed graph model based fuzzy logic. Operating procedure is expressed according to a formal expression. Possible operation deviations from normal operating procedure are identified by using a group of guidewords. Hazards are identified automatically by qualitative simulation and inference when wrong operation process is performed. The method is validated by a rectification column system. Comparing with continuous production process, unsteady operation process, such as startup and shutdown, tends to abnormal large due to a large number of operations of operators and dynamic state changes involved. To guarantee a safe operation, process hazard analysis (PHA) is very important In the chemical process industry, hazard and operability (HAZOP) analysis is the most widely used method. In this paper, based on proposed qualitative simulation and inference method, an automatic HAZOP analysis method for unsteady operation processes is proposed. Mass transfer and relationships among process variables are expressed by Petri net-directed graph model based fuzzy logic. Operating procedures are expressed by using a group of guidewords. Hazards are identified automatically by qualitative simulation and inference when wro ng operation process is performed. The method is validated by a rectification column system.