Hi Matthew,
I'm not sure I understand the question "is it possible to use JBoss Remoting with sockets from within JBoss AS". But I'll try to answer anyway. When you wrote your standalone application, you created a Remoting server by creating an org.jboss.remoting.transport.Connector, right? Well, you can do the same thing by configuring the Connector declaratively in a file in $JBOSS_HOME/server/$CONFIG/deploy. The nature of your file will depend on the version of AS you are using.
I'm not aware of any socket blocking.
Hope that helps. Am I close?
-Ron