FR 2508 then FR 4545 at Barcelona
Cologne → Barcelona → Porto
Timetable, Barcelona time
07:55FR 2508 from Cologne at the gate
20:40FR 4545 to Porto leaves the gate
12 h 45 apart on the timetable
FR 4545 leaves 12 h 45 after FR 2508 arrives on the timetable: more than half a day, so not a connection we count.