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.
This is how cloudflare handles it for normal web services. If you’re coming from trash IPs there is no chance a curl request is going to make it through to a backend without an onerous captcha.
If I saw the Time Warner ASN send too many requests, my first thought wouldn't be to just block a huge ISP. Who knows what mihjt be causing these issues and what you could be breaking by interrupting service.
The Time Warner NOC wouldn't be able to completely fix the problem if the source of the issue is the firmware of a certain shitty IoT device. If someone emailed their NOC about some weird IP cams installed by their customers causing load on their servers, they could feel like that's a problem between icanhazip and the camera manufacturer, not something they can fix.
The author is quite tolerant of the obviously malicious behaviour others are attacking his servers with. I'd have taken more aggressive measures instead of scaling up capacities myself. Because the problem is volume and not necessarily anything complex, I'd wager that even a simple block could be quite expensive because that traffic and the associated retries will be going somewhere. Directing the traffic towards the last router in their ASN through DNS would be something I'd consider, making it the problem of the network operators.