I see only one subscription listed in their account. Each subscription allows 2 PC activations. Is it possible there was some confusion about this when they purchased?
I have also contacted our order fulfillment team to check again and make sure they are not missing a subscription.
For the problem refreshing the license, please try the Refresh command listed in the following article:
It may be necessary to manually launch the ansysls_client.exe file using Run as Administrator before the process will work as described in the article.