Across the Pyrenees in one day avoiding auto routes is a lot of riding.
This is only a suggestion have a look on google maps and decide for yourself your preference if this isn't what you want.
San Sebastian
NA-4150
NA-170
N-121-A
Pamplona
A-21 <-- I know you want to avoid auto routes but this one will save time and not too long.
Jaca
N-260 for as long as you wish then head south on either C-13 or C-14 towards Tarragona
Google maps directions is giving roughly 10 hours to complete taking C-14 may be less time on C-13.
Right, i have plotted the following for my forthcoming trip given the time frame etc. Now I know it will not meet some peoples approval but I am happy with what I have chosen bearing in mind that I have not ridden in Europe for some 40 years!!
So here goes;
Day 1 the boring bit Perthshire to Newhaven for ferry and the longest day in the saddle!!
Day 2
Dieppe
Rouen
LeMans
Tours
Potiers
Angouleme
Day 2
Angouleme
Pau
Arudy
Laruns
Biescas
Sabinanigo
Huesca
Zaragoza
Day 3
Zaragoza
Teruel
N330 Utiel
Requena
N330 Almansa
CM3220/CM426 Yecla
Jumilla
Pick up A33 towards Murcia A30/ Pick up A7 - E15 to RM 2 Leave at either junct 14 or 26 to Fuente Alamo.
All plotted on garmin ready to download to sat nav fingers crossed that it all works!!! If not it's back to the old faithful Michelin maps!?!?!
After two weeks lounging around the pool and beach it's all done in reverse.