I've been thinking about this and haven't seemed to tie it all together, perhaps if I post this someone else will be able to pull it together (Morten, Pete?).
Start out with your initial P, T and level in the drum. Calculate the mass of liquid and vapor (you'll use this later). Now, as the fire heats up the liquid, it follows the vapor liquid phase envelope until it reaches the critical point and becomes a supercritical fluid. Now, at this point, the volume for the fluid is the vessel's volume. The mass is the sum of the initial vapor and liquid masses so you know the density in the drum. You can plot this on the Mollier diagram and you know as the fire continues to input heat into the system raising the pressure and temperature, that you HAVE to follow along a constant density line (since the volume effectively isn't changing and the mass is fixed). At the relieving pressure, you can then use the Mollier chart to scale off the relieving temperature (correponding to the 'fixed' density at the relieving pressure).
Where I seem to have a disconnect is at the critical point, you should also be at the critical density (?) and how do you then 'jump' to the density you've just calculated you need to have?
Anyway, assuming we work this out AND I'm right %- Then, flash this mixture to the outlet pressure. Looking at the Mollier chart, I'm pretty sure you'll have 100% vapor and you can size the valve for a vapor relief. Watch your Z (which can be back calculated from the density, pressure and temperature), if it's below 0.5, you might want to consider a minimum 'effective' limit as Zs can be somewhat sensitive and directly affects the required area.