If the vessel is stamped with an MAWP of 100 psi, then you are not allowed to operate above 100psi.
The relief valve should be set to relieve at 100psi.
This is a fairly low pressure, and the vessel is likely able to operate at a pressure above 100psi. However, to do this you would need to have the vessel re-rated for a higher MAWP. This would involve preparing calculations for a higher pressure to ensure nothing needs to change with the geometry, re-hydrotesting the vessel, then having the re-rating documented (in North America this would be done as an alteration under the rules of the National Board Inspection Code (NBIC), and signed off by an Authorized Inspector).
Cheers,