Pressure is building on Spain to recognise Catalan province’s move for independence from the Madrid government after 90 per cent of voters in an unauthorised independence referendum backed the break.

Catalan residents took to the polls and the streets throughout Sunday in a day of chaos that saw at leat 844 civilians injured by Spanish riot police.

Police smashed their way into Catalan polling stations to try to halt a disputed referendum on independence, while rubber bullets were fired into demonstrating crowds and voters were attacked during the daylong melee.

Spanish Prime Minister Mariano Rajoy insisted there was no independence referendum in Catalonia and praised police, saying they acted with “firmness and serenity” in response to the vote.

Police broke down doors on Sunday to force entry into voting stations as defiant Catalans shouted “Out with the occupying forces!” and sang the anthem of the wealthy northeastern region.

Officers in riot gear hit people with batons and forcibly removed would-be voters, including women and the elderly, from polling stations.

The referendum, declared illegal by Spain’s central government, has thrown the country into its worst constitutional crisis in decades and deepened a centuries-old rift between Madrid and Barcelona.

“On this day of hope and suffering, Catalonia’s citizens have earned the right to have an independent state in the form of a republic,” Catalan governor Carl Puigdemont later said in a televised address.

“My government in the next few days will send the results of today’s vote to the Catalan Parliament, where the sovereignty of our people lies, so that it can act in accordance with the law of the referendum,” he said.

Despite the heavy police action, hundreds-strong queues of people formed in cities and villages throughout the region to cast their votes.

At one Barcelona polling station, elderly people and those with children entered first.

Mr Puigdemont called on Europe to step in to make sure fundamental rights were fully respected.

In a sign tensions will endure beyond the vote, secessionist groups and trade unions in Catalonia have called a general strike for Tuesday, La Vanguardia newspaper reported.

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The ballot will have no legal status as it has been blocked by Spain’s Constitutional Court and Madrid for being at odds with the 1978 constitution.

The region of 7.5 million people has an economy larger than that of Portugal.

The Catalan government said voters could print out ballot papers at home and lodge them at any polling station not closed down by police.

Catalan leader Carles Puigdemont accused Spain of unjustified violence in stopping the vote and said it created a dreadful image of Spain.

“The unjustified, disproportionate and irresponsible violence of the Spanish state today has not only failed to stop Catalans’ desire to vote … but has helped to clarify all the doubts we had to resolve today,” he said.

The Madrid government said 11 police officers were injured in the clashes.

Mr Rajoy said the people of Catalonia had been tricked into participating in the banned vote.

“Today, we have not had a referendum for self-determination in Catalonia. Today, all the Spaniards have seen that our state rule of law keeps its strength and reality, and restricts those who wish to subvert the state of law,” he told a news conference on Monday morning (AEST).

“We have seen behaviours and attitudes that are repugnant to any democrat, and never again shall be repeated.

“I want to be absolutely clear that those responsible for the events that have taken place today are the responsibility of those who have promoted the violation of legality and breach of convivance.”

Nicola Sturgeon, the pro-independence leader of Scotland, which voted to remain part of the United Kingdom in a 2014 referendum, said she was concerned by the images she was seeing from Catalonia.

“Regardless of views on independence, we should all condemn the scenes being witnessed and call on Spain to change course before someone is seriously hurt,” she said on Twitter.

Belgian Prime Minister Charles Michel tweeted: “Violence can never be the answer! We condemn all forms of violence and reaffirm our call for political dialogue.”

Around 70 polling stations had been raided by police, Spanish Interior Minister Juan Ignacio Zoido said.

The aim of the raids was to seize referendum material and not to target people wanting to vote, another senior government official said.

Spain’s Deputy Prime Minister Soraya Saenz de Santamaria said police had acted in a proportionate manner.

“We have been made to do something we didn’t want to do,” said Enric Millo, the central government’s representative in Catalonia, at a news conference.

A top-flight Spanish soccer match between Barcelona and Las Palmas on Sunday will be played without any supporters in the stadium because of the unrest, the Catalan club said.