Keeps asking me for serial number when starting up program and when entered it tells me it's not a valid serial number, but it's the one that came with my software

I purchased CS6 Design and Web Premium through the Department of Education Australia just over a year ago and now I can no longer access my software. It keeps asking me for my serial number, but when I enter the serial number that came with the product it tells me it is invalid???

Check with the school to make sure the licensing should still be valid.  Some school make arrangements only for temporary licensing.
You can also try checking with Adobe Support thru chat.
For the link below click the Still Need Help? option in the blue area at the bottom and choose the chat option...
Serial number and activation chat support (non-CC)
http://helpx.adobe.com/x-productkb/global/service1.html ( http://adobe.ly/1aYjbSC )

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