There are instructions to deploy COPS (Calibre OPDS) in a Synology, it doesn't provide all the functionality that Calibre Companion does, but it's ok for downloading. If you want to access outside your wifi, security is non existent or difficult to implement, I can't remember now if it was possible, so probably only workable inside your wifi.
You have also Bicbucstriim project, latest version is from 16/11/2018, so I don't know if it's still maintained and if it'll work with latest versions of Calibre.
And depending if your Synology is potent enough to work with Docker, you might install a docker image of Calibre and have the Calibre Web activated 24/7.
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