The risk assessment of thermal hazard to identify chemical or process hazard during early process developments have been considered. The early identification of thermal hazards associated with a process, such as rapid heats of reaction, exothermic decompositions, and the potential for thermal runaways before any large scale operations are undertaken. This paper presents to evaluate the safe operating parameters/envelope for exist plant operations. The assessment of thermal hazard with operating conditions such as amount of process materials, inhibitor, and catalyst on esterification process in manufacture of concrete mixture agents are described. The experiments were performed by a sort of calorimetry with the Multimax reactor system as a screening tool. The aim of the study was to evaluate the thermal risk of process material and mixture in terms of safety security to be practical applications in esterification process. It suggested that we should provide the thermal hazard of reaction materials to present safe operating conditions with cause of accident through this study.