Currently, Dali does not provide support for validating your JPA configuration outside of an Eclipse workspace. (Dali has lots of dependencies on other Eclipse plug-ins.) That's a good idea, though. Perhaps you could submit an enhancement request via Eclipse's Bugzilla[1].
That said, you could use EclipseLink's Integrity Checker to validate your settings against a live database. See these links: [2] and [3]. If you are using another JPA implementation, it is possible it also provides a way to perform validation.
[1] https://bugs.eclipse.org/bugs/enter_bug.cgi?product=Dali%20JPA%20Tools
[2] http://wiki.eclipse.org/EclipseLink/Examples/JPA/IntegrityChecker
[3] http://wiki.eclipse.org/Configuring_a_Session_%28ELUG%29#Configuring_the_Integrity_Checker