I have not found a way to "Send for Signature" using a file from the DC library from within the desktop Acrobat Pro DC. From the mobile app and the web GUI, you can choose a file from many sources, including the Library. But from the desktop, you can only choose a local file when using "Send for Signature". Once you have one file from local, then you can add one from the library, but there does not seem to be any way to just send one from the library by itself.
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