FR 2508 then FR 4585 at Barcelona
Cologne → Barcelona → Porto
Timetable, Barcelona time
07:55FR 2508 from Cologne at the gate
06:55FR 4585 to Porto leaves the gate
23 h apart on the timetable, overnight
FR 4585 leaves 23 h after FR 2508 arrives on the timetable: more than half a day, so not a connection we count.