Well Zoro will probably spare his life unless Mihawk will ask him to be killed then I don't know how Zoro would react to such a staggering demand. If not, I doubt Shiryu will kill Mihawk as I don't see any interlinking between the two. Of course only atm.
It would fundamentally depend on what's intended obviously.
Officially merely when the vivre card does suggest so or at least the manga officially recognizes him as such in a convincing way.
More practically the very moment he surpasses him independently.
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