use a cookie:
when the form is sent, also send a cookie
with variable 'sent=0';
place a hidden variable 'sent' in the form with a random value
When the form is sent, check that the value of cookie 'sent'.
If it is 0, put the new random value in the cookie and process the form -- sent=12345
If it is 12345 ($COOKIE['sent']==$POST['sent']) don't process the form and display some friendly error page.