If you want to collect e.g. PDF files with invoices from a folder, that are waiting to be sent to a customer as multiple attachments in a single email, then you should consider example 1, which is shown for the workflow component, List filesystem. There is also a suggestion for an add on in example 2. Direct file access is a prerequisite for this solution.
If file access is not an option and you still want to collect multiple PDF files found in a folder and add them as multiple attachments in a single email, then you can consider to save the files as resources e.g. in the other folder of the Library. Then you should consider the workflow component, List resources and build a workflow similar to what is shown in example 2.