To demonstrate what I mean the attached XML file is for one smiley, :D, which by default is already assigned to Big Grin on a fresh XF install. For the purpose of testing it has been assigned to a category named "Don't Worry, Be Happy" in the XML. Attempting to import using the XML file will give an error message. Going back to your smilies page you will now see an empty "Don't Worry, Be Happy" category. Go back and try to reimport the XML file again. This time change the :D replacement text to something unique so you don't get an error. Go back to your smilies page and now you will see a second "Don't Worry, Be Happy" category.
For any admins who tend to have a lot of smilies .... .... I think there are two things at play here. The first is that if the category in the XML file already exists then it should use the existing category instead of creating a duplicate one with the same name -- just think of the cleanup an admin will have to do every time they import an XML collection with the category name "Star Trek" in it. The second is that it shouldn't create the category unless at least imported smiley request is valid to be imported -- because you are not preemptively warned that the replacement text is already in use, if it takes you a few tries to get it imported you'll end up with several duplicate empty categories to be cleaned up.
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