Either the expansion vessel is burst internally or more likely the hose going to the expansion vessel is choked solid. The system then keeps expanding and blows water out the prv because the blockage means the system water has no other means of expansion. You have to drain the system and remove the hose, the problem with that is there is a lot of pressure built up behind the blockage and it can get messy when you disconnect it, hot water can shoot out at 3 bar so wrap an old towel round the connection as you disconnect it and wear old clothes that won't matter if you get soaked with dirty water! Clear the blockage in the hose with a long thin screwdriver or wire, reconnect and check the vessel air pressure is ok, refill the water and you should be fine after that! Hope this helps.
Taliskerman
March 2011