Can thralls use siege cauldrons?

It allows me to place thralls onto them? Does this mean theyll use them when enemies are under it?

yes its was a thing their came out in age of war

Yes, but be certain the cauldron has tar in it for ammunition. The supply does get expended as the thralls tip it.

Thralls also can work the burning cauldrons.

Oh yes.
And as LostBrythunian pointed out, make sure they have “ammo”.

That’s one of the few times I can honestly think to myself as those wretched purge enemies come to our personal bank to make unauthorized withdrawls …
“Come on baby, light my fire”. (Attributed to the rock band, “the Doors” - “light my fire”).