I don't know if Hibernate can support this mode of operation (perhaps though some creativity), but there are a couple of other products that might provide what you need:
Prevalyer is a transparent persistence framework that behaves like a giant in-memory cache, although it does so with some tradeoffs. Its home is at
http://www.prevayler.org/ (although the site appears to be down right now.
Also, GemStone used to offer a transparent persistence "fabric" with their app server. The company has changed hands and directions since then, but it appears they still have similar produts. However, GemStone is enterprise-class software and priced accordingly.
Hope this helps (please give credit if it does),
Eric