To my knowledge, NCAA does not allow a player to change jersey number, unless necessitated by damage or blood. She's just not allowed to play while wearing the different number. (Unlike NFHS rules, which allow a player to be listed on a roster with a regular number and a libero number.)
Out of curiosity, was her "new" number listed as the libero's number on the line-up sheet?
If it's not discovered until after the beckon for serve, the penalty would be a point to the opponent for having an illegal player on the court. There's no way I would DQ her. Even if I thought she did it to try to cheat, I would only go with a red card, personally.
I'm willing to be corrected.
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