More than 460 people have been injured in disturbances across Catalonia on Sunday, the Barcelona mayor said, as riot police cracked down on attempts to hold a banned referendum on Catalan independence from Spain.

“As mayor of Barcelona I demand an immediate end to police charges against the defenceless population,” Ada Colau said in a statement.

In a separate statement, the Catalan health service said 465 had been hurt, with two in serious condition in hospital.

Spanish riot police burst into polling stations across Catalonia confiscating ballot boxes and voting papers to try to halt a banned referendum on a split from Spain as Madrid asserted its authority over the rebel region.

Police broke down doors to force entry into voting stations as defiant Catalans shouted ‘Out with the occupying forces!” and sang the anthem of the wealthy northeastern region. In one incident in Barcelona, police fired rubber bullets.

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.

People raise their arms in front of Spanish police after the seizure of ballot boxes in a polling station in Barcelona. Photograph: Pau Barren/Getty Images

Despite the 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.

“I’m so pleased because despite all the hurdles they’ve put up, I’ve managed to vote,” said Teresa, a 72-year-old pensioner in Barcelona who had stood in line for six hours.

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.

Catalonia’s High Court said on Sunday that courts in the region had received several complaints over the local police’s failure to close polling stations despite orders to enforce a judical ban on the referendum.

Cattalan firefighters protecting crowd and standing against Spanish riot police. #CatalanReferendum pic.twitter.com/oNzH5GchJY — Fuad Alakbarov (@DrAlakbarov) October 1, 2017

Elderly woman seriously injured after being hit by Spanish riot police. #CatalanReferendum pic.twitter.com/ynfXAr3Pxz — Fuad Alakbarov (@DrAlakbarov) October 1, 2017

Didn't understand it fully before today, but I now see why Catalan wants to be free of Spain.#CatalanReferendum pic.twitter.com/1OH1fWDRPc — Gissur Simonarson (@GissiSim) October 1, 2017

An elderly woman is removed by force as police move in on the crowds.Photograph:David Ramos/Getty Images

A minority of around 40 per cent of Catalans support independence, polls show, although a majority want to hold a referendum on the issue. The region of 7.5 million people has an economy larger than that of Portugal.

However much voting takes place, a “yes” result is likely, given that most of those who support independence are expected to cast ballots while most of those against it are not.

Large crowds

Organisers had asked voters to turn out before dawn, hoping for large crowds to be the world’s first image of voting day.

A woman casts her ballot as she votes in the referendum at Escola Collaso I Gil public school polling station. Photograph: Dan Kitwood/Getty Images

“This is a great opportunity. I’ve waited 80 years for this,” said 92-year-old Ramon Jordana, a former taxi driver waiting to vote in Sant Pere de Torello, a town in the foothills of the Pyrenees and a pro-independence bastion.

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

Elsewhere, people were not able to access the ballot boxes. In a town in Girona province where Catalan leader Carles Puigdemont was due to vote, Civil Guard police smashed glass panels to open the door and search for ballot boxes.

Spanish police clear the entrance of a polling station in Barcelona. Photograph: Pau Barrena/AFP/Getty Images

Puigdemont voted in a different town in the province. He 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 government said 11 police officers were injured in clashes.

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.

“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.

People wait to cast their ballot in the referendum vote at Escola Industrial of Barcelona school polling station. Photograph: Chris McGrath/Getty Images

One analyst said the scenes being played out across Catalonia on Sunday would make it harder for Madrid and Barcelona to find a way forward.

“I think it is going to make the clash more intense and make it more difficult to find a solution,” said Antonio Barroso of Teneo Intelligence.

Puigdemont originally said that if the “yes” vote won, the Catalan government would declare independence within 48 hours, but regional leaders have since acknowledged Madrid’s crackdown has undermined the vote.

Markets have reacted cautiously but calmly to the situation so far, though credit rating agency S&P said on Friday that protracted tensions in Catalonia could hurt Spain’s economic outlook. The region accounts for about a fifth of the economy.

Reuters