That's not true. PNG has some filters that pre-compress the image before sending it to zlib.
The png optimizers you see (optipng, pngcrush, etc)? What they do is carefully pick the optimum filters to get the best file size. So I'd say those filters were the most important part of the compression.
http://www.smashingmagazine.com/2009/07/15/clever-png-optimi...