Keep in mind that water and steam are the same chemical, and that for thermal events you have generated steam. Also, pressure is temperature for steam. I know these are tough to "wrap your head around" when empirically looking at a system. I've got a BUNCH pf PRV's that some engineer rerated to liquid flow, just because they were in process or cooling water service. Except he/she failed to note that the relieving temperature was 300-400°F. No longer a liquid.
The only time you should worry about relieving at a particular temperature [vs. pressure] is if your PRV is too small to vent at a rate sufficient for vapor. Best example are the Pressure /Temp Safety Valves on hot water heaters in the USA. They are small, but they relieve at, or just below the boiling point of water -- temperature-activated vent. So the relieving volume is much smaller -- steam occupies 1600X the volume of liquid water.