You have two problems. Firstly, the first time you set the value of the time() session, so the first attempt will always lead to exceeding the limit. The second problem is that you have a typo in $_SESION .
Try:
session_start(); if (isset($_SESSION['last_submit']) && time()-$_SESSION['last_submit'] < 60) die('Post limit exceeded. Please wait at least 60 seconds'); else $_SESSION['last_submit'] = time();
It should also be noted that this is not reliable, as users may refuse cookies or delete a session cookie to bypass the validation.
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