maddocks:
A "simple thermal" pressure relief valve works only on contained liquids (or non-compressible fluids). It is not applicable to gases or vapors. Therefore it does not apply to your scenarios - unless you need to consider the case where the entire KO drum is 100% liquid-filled and subjected to a fire case while it is blocked-in. I don't think that this is one of your credible scenarios.
Briefly, you have to establish the identity of all the possible, credible over-pressure scenarios that can occur on the KO drum. Once you have identified them (including the fire case), then you have to quantify the amount of PSV capacity required in each scenario to avoid an over-pressurization of the KO drum. The worse-case scenario is your design case for the PSV. That is how you decide the size of the PSV required.