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Definition of anneal:
When you anneal metal or glass, you heat it and then cool it in order to make it less brittle and more malleable.
Is it explicitly used for metals and glass? Can I use to describe intensity of training such as
Chinese coaches annealed children for Olympics
By saying this I want to emphasise on rigours training they gave to the children. Is this proper?
English is a language that loves metaphor, so you definitely have the right idea. There is nothing wrong with using a phrase meant to apply to physical materials as a metaphor for some human process, and of course writing style is very much a matter of personal choice. However, as with any language, not every word is appropriate for every context.
The problem I see with "anneal" is that it's not often used, and so the meaning might not be clear to your audience. As I said, there's nothing wrong with it, but you might consider that there are already common expressions to describe what you want to say:
He was forged by merciless training and strict discipline.
Her will became hardened like diamond from the continual stress of the internship program.
A few months in the military hammered his body into solid steel.
As well as many others. This is the ongoing challenge for any writer -- to pick exactly the right word to accurately convey what you want to express.
Training : Children :: Annealing : Metal.