A hostile reply from a netblock operator seems like a perfectly valid reason to block their traffic.
That being said, a service like this doesn't come with any guarantees and if it'd disappear from the net tomorrow, I wouldn't blame the author. Blocking is a perfectly valid solution to this problem, but assuming malice isn't always the right answer.
Were I in this situation, I'd rate limit networks per /24 (maybe even /16?) as much as I could, and work together with antivirus companies to help identify infections of malware known to use the service to discourage criminals from abusing the system. I wouldn't even bother hosting the site on IPv6 since those addresses are supposed to be public anyway. The author clearly has more patience than I do.
At the HTTP level it's probably cheaper to just return the HTTP 200 response. I suppose if you're doing TLS handshakes then a packet-level rate-limit would help significantly, but at the same time I'd be wary of triggering any kind of retry-behavior.
Worst-case scenario for a service like this would be having an error response/timeout trigger some kind of unlimited retry flood.
I probably wouldn't bother with TLS either, just a plain HTTP 0.1 response with minimum information should be enough.