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Under the library icon you can direct the unportable instance of calibre to find the library in the portable folder, if that portable drive is connected. It's the Switch/Create Library command, and the option to use the previously existing library at the new location which you can navigate to with the computer button to right of New Location box.
Don't write to the same library from 2 different instances of calibre either, as a general rule. In the case of copy to library, I'm not sure, that might be an exception.
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