HI,
I have a friend in Cape Town, South Africa with a full matriculation certificate, that is wanting to come over to the UK to study further. She has a duel citizenship as she is Portuguese and has full citizenship in Portugal, Madeira as well as full citizenship in South Africa. The problem I am struggling with is whether it is possible for her to come over to the UK, live with family/friends within the UK, attend a college then university and still apply for EU benefits within the UK as an EU student?
She is able to work and study.

If she has a Portuguese citizenship, she is automatically a member of the EU, so same rules that apple to anyone in the EU apple to her. She can travel to the UK without a visa, she can probably study and work there according to the EU agreements.