The PRV value is printed on the top of the red knob, they come with the calorifier as reccomended by the manufacturer, values are 1bar, 2bar, 2.5bar and 3 bar in the marine world so have a look at the one you have to get another.
The max PRV supplied from most manufacturers is 3bar.
Look for lime scale or other items of crud in the valve seating that may stop it from shutting down fully.
Has the PRV valve spring weakened? it is rare for these to fail.
your water pump pressure should not be too high, otherwise the PRV will blow off sooner than it should as the pressure builds up when the water gets hot.
A water pump with about 1.4 bar cut off pressure is better for calorifiers.
Julian is correct with the pressure when used as a Accumulator Tank, we set them between 7 and 15 psi when used with a 1.4 bar (20psi) cut off, NO MORE!
However, when used as an Expansion Tank we follow the instructions as supplied with the tank, that is: The tank is supplied charged with nitrogen gas at about 2.3 bar (35psi). The pressure should be adjusted to the CUT OFF pressure of the pressurised water pump. This should be done before the tank is installed. N.b, This is just one section of the booklet supplied with the tanks. reccomend you obtain the full copy to fully clear the air!