She should be able to get the Chinese visa on the same day with special service (but pay extra $) if she can go to the Chinese Embassy.
If she uses the Chinese passport she may be lucky to get out and get in without trouble, but things can not be expected, even in China. Since her Chinese passport is not valid any more if anything happens she could be in big trouble. Very few people would take such a risk.
In any case if she starts use one passport she should use that passport until she returns to where she starts.