If I supply 24v to a 50v rated 22000uf electrolytic capacitor, does that mean it will store 44000uf at 24v?
If you exceed the voltage rating of the capacitor, the capacitor may fail.  

If you put 24V across a cap, it will charge to 24V. 

If it's spec'ed at 22000uF it's 22000uF for ANY voltage.