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It is possible to upgrade, but you need to configure some stuff. You need to install new soft in another home, configure instance, run in upgrade option, recreate catalog (catalog.sql, catproc.sql), etc. If it isn't big database consider duplicating it using RMAN. It probably can be faster, and for sure it will be safer
I suggest you install enterprise editiion and defenitely conventional export/import will work for you without any hassle.
Just export / import application based schema
On SE exp system/password owner=userA,userB, userC, userD file=myusersexport.dmp log=myusersexport.log On EE, make sure userA, userB, userC, userD exists and so any special ROLES before importing imp system/password fromUser=userA,userB,userC,userD toUser=userA,userB,userC,userD file=myusersexport.dmp log=myusersimport.log
I was able to get my database up and running simply by un-tarring the enterprise edition of Oracle into my $ORACLE_HOME directory. The database came up normally and I was even able to enable Enterprise Edition features, e.g. Oracle Streams.
What are the pitfalls from not rebuilding the database under EE?
Actually, I just found an article that says you don't have to do anything special to move to EE from SE as long as they're the same version:
Moving From the Standard Edition to the Enterprise Edition
If you are using the Standard Edition of the Oracle Database and want to move to the Enterprise Edition, then complete the following steps:
1. Ensure that the release number of your Standard Edition server software is the same release as the Enterprise Edition server software.
For example, if your Standard Edition server software is release 10.2.0, then you should upgrade to release 10.2.0 of the Enterprise Edition.
2. Shut down your database.
3. If your operating system is Windows, then stop all Oracle services, including the OracleServiceSID Oracle service, where SID is the instance name.
4. Deinstall the Standard Edition server software.
5. Install the Enterprise Edition server software using the Oracle Universal Installer.
Select the same Oracle home that was used for the de-installed Standard Edition. During the installation, be sure to select the Enterprise Edition. When prompted, choose Software Only from the Database Configuration screen.
6. Start up your database.
Your database is now upgraded to the Enterprise Edition.