Three people have been arrested – including a young girl, for disobedience and assault, the ministry said.
The Catalan health service have confirmed that two people are in serious condition in hospital.
And 319 polling stations have been closed by cops across Catalonia.
The referendum today has been branded “illegal” by Madrid but Catalan authorities insist they will declare independence from Spain in the event of a “yes” vote.
Despite the dramatic scenes, Spanish Prime Minister Mariano Rajoy suggested the protests had been for nothing in a dismissive statement.
But the region is faced with days of disruption as independence groups refuse to accept Rajoy’s stance.
Trade unions and pro-independence groups have called for a general strike in Catalonia on Tuesday, paving the way for yet more uncertainty.
He slammed the vote as “illegal” and said the majority of protesters were fooled into taking part.
Rajoy said: “So many Catalans have been cheated when they were invited to participate in an illegal mobilisation.
“I understand the frustration that today can be felt and I really regret that the people affected by this suffer.”
He said the protests were a strategy against legality and democracy and thanked the police for cracking down on those involved.
Rajoy added: “The vast majority of the people of Catalonia did not want to participate in the secessionists’ script.
“They have shown that they are law-abiding people and quietly ignored the call.”
The Prime Minister has been branded a “dictator” by other politicians after his controversial address.
Venezuelan President Nicolas Maduro said: “Rajoy has chosen blood, sticks, blows and repression against a noble people. Our hand goes out to the people of Catalonia. Resist, Catalonia!”
Earlier today, cops were forced to fire rubber bullets and use batons on Sunday to prevent riots from breaking out on the streets during the illegal votes.
Emergency services attended to the voters injured as officers stormed voting stations to stop the banned referendum.
Spanish Deputy Prime Minister, Soraya Saenz de Santamaria, praised the actions of cops to prevent the votes going ahead in Catalonia.
The “absolute irresponsibility” of the Catalan regional government in holding the vote had been compensated for the professionalism of the Spanish security forces.
She said: “They have compiled with the orders of justice. They have acted with professionalism and in a proportionate way.
“They have always sought to protect rights and liberties.”
The Catalan leader claims the “unjustifiable violence” in the banned referendum has created a terrible image of Spain.
For the full article visit: http://www.dailystar.co.uk/news/world-news/648945/Catalonia-Spain-Independence-referendum-vote-riots-violence-European-Union-EU-politics