blocking a website even with vpn

Not exactly. You can block ports used for the tunneling protocols..
TCP:
1723, 47
UDP:
500, 1701

Many use web ports so... might not work

You can block openVPN but not sslVPN so it probably isn't even worth bothering with.

even if you eliminated admin rights, proxies are trivial to set up, and if they are using a proxy to "VPN" to their home internet, you're going to have one heck of a time preventing it.