Reactive hazard associated with chemicals is a major safety issue in process industries. This kind of hazard has caused the occurrence of many accidents, leading to fatalities, injuries, property damage and environment pollution. Reactive hazards can be eliminated or minimized by applying Inherently Safer Design (ISD) principles such as "substitute" or "moderate" strategies. However, ISD would not be a feasible option for industry without an efficient methodology for chemical hazard assessment, which provides the technical basis for applying ISD during process design. In this research, a systematic chemical hazard assessment methodology was developed for assisting the implementation of ISD in the design of inherently safer process. This methodology incorporates the selection of safer chemicals and determination of safer process conditions, which correspond to "substitute" and "moderate" strategies in ISD. The application of this methodology in conjunction with ISD technique can effectively save the time and investment spent on the process design. As part of selecting safer chemicals, prediction models were developed for predicting hazardous properties of reactive chemicals. Also, a hazard index was adopted to rate chemicals according to reactive hazards. By combining the prediction models with the hazard index, this research can provide important information on how to select safer chemicals for the processes, which makes the process chemistry inherently safer. As part of determining safer process conditions, the incompatibility of Methyl Ethyl Ketone Peroxide (MEKPO) with iron oxide was investigated. It was found that iron oxide at low levels has no impact on the reactive hazards of MEKPO as well as the operational safety. However, when iron oxide is beyond 0.3 wt%, it starts to change the kinetics of MEKPO runaway reaction and even the reaction mechanism. As a result, with the presence of a certain level of iron oxide (> 0.3 wt%), iron oxide can intensify the reactive hazards of MEKPO and impose higher risk to process operations. The investigation results can help to determine appropriate materials for fabricating process equipment and safer process conditions.

The integration of the safety parameter into process design and optimization is essential. However, there is no previous work in integrating the fire and explosion index (F&EI) into design and optimization. This research proposed a procedure for integrating safety into the design and optimization framework by using the safety parameter as optimization constraint. The method used in this research is Dow’s Fire and Explosion Index which is usually calculated manually. This research automates the calculation of F&EI. The ability to calculate the F&EI, to determine loss control credit factors and business interruption, and to perform process unit risk analysis are unique features of this F&EI program. In addition to F&EI calculation, the F&EI program provides descriptions of each item of the penalties, chemicals/materials databases, the flexibility to submit known chemical/material data to databases, and material factor calculations. Moreover, the sensitivity analyses are automated by generating charts and expressions of F&EI as a function of material inventory and pressure. The expression will be the focal point in the process of integrating F&EI into process design and optimization framework. The proposed procedure of integrating F&EI into process design and optimization framework is verified by applying it into reactor-distillation column system. The final result is the optimum economic and inherently safer design for the reactor and distillation column system.