I think on re-reading some of these posts thatwe have all come to the same conclusion. I think Clamont that you are putting the cart before the horse in your statement "...above the design pressure which is determined by the opening pressure of the PVRV." This is the wrong way round. The design presusre is calculated according to Appendix F section 4.1, 4.2 and 4.3, with the lower of these calcualtions being the design pressure. According to section 5.8.5.3, as IFRs says, the emergency venting pressure shall not exceed the design pressure calcuated in either F4.1, 4.2 or 4.3. The only exception to this is if the tank has been designed to have a frangible roof joint (i.e. the roof lifts off in an emergency (!!)).
Once you've worked out your design pressure from 4.1 to 4.3 or use the stated (name plate) design pressure by the tank designer (if known), then you set your vent pressures accordingly to allow "normal" venting to occur, but with sufficient margin to allow activation of the emergency venting, but always less than or equal to the design pressure of the tank. This calcualted using the vendors accuracy limits. Your statement above seems to say that you believe the current PVRV is set at the design presusre or are you making an assumption? If the PVRV is set at the design presusre, then you will need to lower it so that the emergency vent can be set above the normal vent pressure so that the design pressure is not exceeded.
In respect of the 33% figure you mentioned, maybe someone applied the 33% over pressure allowed within the B31.3 piping code which is permitted for leass than 10 hours and no more than 100 h/yr? I've seen people mix and match design codes before, but this is not permitted.
My motto: Learn something new every day
Also: There's usually a good reason why everyone does it that way