You could open up the preference file at:
~/Library/Preferences/com.omnigroup.OmniWeb5.plist
and add your black list entries this way. They black list is kept in the "OWAddressesToFilter" key.
You'll need a plist editor to edit this. One comes with the Apple Developer Tools or you could get PlistEdit Pro:
http://homepage.mac.com/bwebster/plisteditpro.html