I'm not sure I can give an example of knowledge that is intrinsically valuable. It depends on your moral value system - the system by which you ascribe "value" to things.
If I take a purely Utilitarian view then it can be argued that only things which promote happiness have value, and in this respect knowledge would have to have some practical or instrumental value for it be valuable.
There are plenty of other schools of philosophy which place value on non instrumental or at least non directly instrumental things, such as truth, beauty, friendship and wisdom.
The example given elsewhere of potentially intrinsically valuable knowledge is friendship. Can it be said that I would get value from the knowledge that someone is my friend, even if it is of no instrumental value at all, for example I know x is my friend (this is a justified true belief) but I never have any subsequent contact with x so they don't do me any favours, or support me emotionally?
Could it not be the case that because I know I have a friend I in effect do get some instrumental value because it makes me happy?