Hello,
What you need to consider is whether the vessel will rupture before the relief valve opens. If the calculated temperature of the contents is correct at 1014 F, then the vessel wall, at a temperature hotter than that, will have a much lower strength than design, so it could fail at a pressure lower than the set pressure. Then you will have a BLEVE (Boiling Liquid Expanding Vapour Explosion) which is extremely dangerous.
I do not understand why the design pressure is so much higher than the relief valve set pressure, however this would have the effect of providing more thickness in the vessel wall, which would help.
In this situation, where there is a large difference between the operating pressure and the relief set pressure, the relief valve will not provide effective protection in a fire, and the vessel should be protected by water deluge and depressurusing (blowdown).
Paul