In order to unlink an account from your Bungie.net Settings Accounts & Linking section, you must log out of Bungie.net and then log in with a different attached account.
You cannot unlink the account you're currently logged in with.
If you have, for example, a Valve Steam account and a Blizzard Battle.net account attached to your profile, you'll need to log out, then log in using the Steam credentials in order to unlink the Battle.net ID.
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Im logged in from steam and the psn button is still greyed out