But Turull and five other separatist leaders have a date at the Madrid-based Supreme Court on Friday, when a judge could indict them on rebellion charges and sent to preventative jail.
Five people were held in custody, including Catalan presidential candidate Jordi Turull who was due Saturday to seek a second round vote in the regional parliament, after failing to be elected earlier in the week.
Rebellion charges are punishable with up to 30 years in prison under Spanish law.
The case against Catalan separatists is now led by Judge Llarena from the Supreme Court, but two other courts, one in Madrid and another in Barcelona, are also investigating officials accused of civil disobedience and other offenses, including organizing the independence referendum held last October, even after it was declared illegal by Madrid.
The court also issued global arrest warrants for six other Catalan figures who have fled overseas, including former regional president Carles Puigdemont.
A judge said the five were serious flight risks.
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Twenty-four protesters were lightly injured in clashes with police, emergency services said.
Later Friday, the Spanish Supreme Court was due to decide whether a separatist candidate for the presidency of the Catalan parliament, Jordi Turull, should also be placed in pre-trial detention.
The deputy leader of the leftwing separatist ERC party, whose chief is now in jail, is now in Switzerland, according to Spanish media.
The decision was met with calls for demonstrations on the streets of Catalonia.
One person who did not appear at the court hearing was Marta Rovira, general secretary of the Republic Left Party.
Llarena also issued global arrest warrants for former Catalan President Carles Puigdemont, who is in self-imposed exile in Belgium along with four of his former ministers.
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Spanish media reported that she had fled into exile in Switzerland.
The court's decision means the vote on Turull's leadership can not go ahead because his presence is mandatory.
But the rulings appeared to inflame the protesters and angry crowds confronted lines of riot police protecting Spanish government buildings in Barcelona.
Catalan parliament speaker Roger Torrent said on Friday he would continue with the session and read a statement in support of pro-independence leaders, despite opposition from the government and unionist parties in Catalonia.
Opposition leader Ines Arrimadas of the Citizens party chided the separatists for not presenting a candidate free of legal problems, which the Spanish government has said is a prerequisite for it ending its takeover of Catalonia's regional affairs.
Following the referendum, the central government in Madrid sacked the Catalan regional government, imposed direct rule and called new elections but pro-independence parties returned with a slim majority.
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