High levels of inhibitor can improve long term storage stability but may be detrimental to operational safety in the case of a fire, loss of cooling, or an external heating induced runaway reaction. The use of high levels of inhibitor can cause the monomer system temperature to far exceed the onset temperature of thermal polymerization under external heating. Once the inhibitor is exhausted, the thermal runaway reaction proceeds at an elevated temperature with a substantial reaction rate and very little reactant/monomer consumption. Loss and excessive use of inhibitor are two scenarios that require evaluation for reactive monomer storage and pressure relief evaluation. Thermal stability information including time to maximum rate, temperature of no return, and self acceleration reaction temperature should be established. This information is required for PSM regulated chemical facilities in order to establish proper safe operating limits as required by the Process Safety Information (PSI) element. This paper outlines the safety and operational considerations and a method for defining chemical reactions and modeling inhibitor effectiveness using Process Safety Office® SuperChems™. Included are two case studies on styrene storage and butyl acrylate runaway incidents.
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