If you are sure that you have correctly downloaded the books to ADE (can you see/read them in ADE?), my guess is that your ADE folder in which the book files reside has changed...did you update ADE? Find the folder that the files are downloading to now and point Calibre to that folder when you are adding.
(The ability to upload the book files to Calibre is independent of DRM. What the OP does with regards to DRM in books from a library is a different discussion.)
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