Cupart,
I just tried out my own procedure on an award booking I have for a pal of mine - and failed, just like you did. It seems that once the FB number is in, there is no way to change it. (Even though it's not his number!)
Previously, though, I have made (cash) bookings for myself on klm.com, whilst logged on to my FB account; when I have then checked the AF website (again, logged on to my FB), the system lists the trip in 'my bookings' but when I look at the details, my FB number is not there - but it then allows me to add it. Weird. And, on a couple of occasions, when I've entered my FB number, I'm told that it is not correct! Even weirder.
-- H