I am also in China and have experienced exactly the same pattern.
We have been using a VPN service through OpenVPN running on our office's servers in France.
Seemingly through DPI techniques, VPN connections are accepted the first time, then within 24 the IP:PORT pattern is blacklisted nation-wide on all internet providers. Since the ban is not "per IP", changing the port helps restoring the connectivity, but only for one more time.
Noteworthy, this affects also VPN servers with very limited user-base. For instance only 2 people in our office have used it at any time. Let me also point out that our purpose is accessing our office's intranet remotely, not browsing otherwise blocked websites.
Since early this year the Obfsproxy project has been started:
https://github.com/isislovecruft/obfsproxy whose goal is to conceal traffic from DPI systems. However, so far Obfsproxy is only bundled with TOR (which is not a solution for our company given the exposure of the exit node).
I would like to hear from OpenVPN devs on ways to use obfsproxy with OpenVPN. Or any other ideas on how to restore a VPN in China.
Please let me know if I can provide you with more supporting documentation or testing logs.