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If you downloaded the file for Kindle for PC and opened it in Kindle for PC and you're using Windows, the file is most likely stored in a folder called My Kindle Content under Documents or My Documents and its name likely starts with B00... or some combination like that. Just import that file to Calibre. (If you have more files there, sort by most recent or something like that.)
Although, yes, as said above, it's probably DRM-protected, in which case Apprentice Alf might indeed be helpful.
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