Hm, strange problem. Check that the name of the file is really "eq2.ini" and not "eq2.ini.txt" (this was already suggested). Make sure your not hiding file extensions when you do this.
To show file extensions, in the Windows explorer got to Tools -> Folder Options -> View and make sure "Hide known file extensions" (or something like that) is NOT selected. That's all i can think of right now. I haven't tried /loadui myself as it's got some problems and the ini-file method should work fine.
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