Rocket - by default, fire sizing calculations are based on the assumption that the vessel/system is blocked in. There's nothing that requires you to apply that assumption - it's just done because (1) it's conservative, and (2) it simplifies the relief load calculation.
I think you're saying your system is open during the fire. That's OK as long as there's good justification for that. With a closed system (default assumption) fire is indeed a dynamic event, unless the system contains a single component. In most cases you're dealing with a mixture, which means the relief composition changes from the beginning to the end. Of course, the relief stream will start off high in light components and then gets heavier with time.
A dynamic simulation model will give you a clear picture of this changing composition, but in most cases I personally don't find that to be worth the time. I look at the composition and choose a conservative component, or mixture of components, to use as a sizing basis. A low Hvap is generally the worst-case for sizing purposes. You can spend a great deal of time doing a dynamic simulation, and come up with an answer that's not significantly different form the answer based on your intuition.
Risk tolerance varies from one company to another, and one individual to another. I think you have to have a very high risk tolerance to say that a dynamic symulation will greatly reduce the size of the PSV. For example, let's say that the dynamic model (changing composition) shows that a P orifice is needed in the early stage of the event and an F orifice is needed at the end. Yes, you can save a lot of money by installing the F orifice. But, to me, what you're really doing is saving money by shifting your risk tolerance, rather than saving money by applying a dynamic model.