Migrants reportedly set light to paper and clothing to ‘attract’ attention and attacked police who came to the scene.
A confrontation between the two groups left nine officers slightly injured at the camp in Murcia.
Authorities are still searching for the group.
Spain’s seven detention centres hold people living in the country illegally until they decide whether or not to deport them.
But there has been a growing number of riots as detainees and critics say the migrants are living in prison-like conditions.
Javier Monje, the Police Union’s spokesman in Murcia, has called for the centre to be closed, saying it ‘cannot stay open a minute more’, adding that police were under equipped.
Some critics blame the deep public spending cuts imposed by Mariano Rajoy and his conservative government, which they say have caused the conditions to worsen.
The SUP (Police Union) has said that when it rains in centres in the south, detainees are told to simply roll their trousers up to their knees.