As been said here before, shooting a artillery round or a mortal shell can detonate it, but the method is not that good because the chances aren't that good. Disposing explosive items by shooting them is a better method when dealing with scatterable mines, for example.
The explosive filler in most shells and rounds takes pretty much energy to go off, that is why most of them have a separate detonator made of more sensitive explosive. This detonator can be a part of the fuse, or it can be a part of the shell. The fuse mechanism causes the igniter to go off, which causes the detonator go off, which in turn makes the explosive filler to go off.
In most cases you need to go for the detonator/fuse to get the round to go off. And if it doesn't go off then you most likely have gotten rid of the fuse, so you are better off when you started.
I am EOD trained and occasionally do disposal work even if it isn't my "primary job". We don't use shooting as a disposal method, as it is not that effective (even if shooting a .50 rifle is always fun), but the method is the primary method for certain types of scatterable mines.
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