Emergency services said 24 people were lightly injured in clashes between police and demonstrators.
Many Catalans went to the streets after yesterday the Spanish Supreme Court chose to sue 25 of the former district leaders who took measures to declare the independence of the area in the autumn of a year ago.
Spain's Supreme Court ruled that 25 leaders of the autonomous region of Catalonia should be tried for rebellion, embezzlement, or disobeying the state. If convicted they would be threaten to serve 30 years in prison.
Several Catalan politicians have fled Spain to avoid being put in jail, including former Catalan President Carles Puigdemont, who fled to Belgium in October.
The woman deputizing for the jailed Junqueras as leader of the pro-independence Catalan Republican Left (ERC) party, Marta Rovira, was also among those indicted, but failed to appear in court on Friday, saying in a letter that she too had chose to take "the path of exile".
Spanish Judge Pablo Llarena ordered detention without bail for Jordi Turull, the president of Catalonia's regional government, former regional legislators Josep Rull, Raul Romeva and Dolors Bassa, as well as the ex-president of the parliament, Carme Forcadell.
Llarena said the five detainees posed a serious flight risk and could seek to push ahead with their plans for unilateral independence if allowed to remain at liberty.
The escalated legal action against the separatists follows Catalonia's independence referendum last October, which the Spanish courts declared illegal.
Demonstrations also took place in other parts of Catalonia.
This would entail fewer calls for engagement with Madrid and the heightening tensions between the regional and federal governments.
Earlier, representatives of the parties standing for Spain's territorial integrity also demanded to cancel the vote. She issued a letter explaining why she had chosen "the path of exile", but Judge Llarena later added her name to his list of worldwide arrest warrants.
The ruling also covered Puigdemont's former deputy, Oriol Junqueras; pro-independence civil society campaigners, Jordi Sanchez and Jordi Cuixart and former Catalan interior minister, Joaquim Forn.
Since then, Mr. Rajoy has repeatedly called on the separatists to form a new government that recognizes Spanish sovereignty and is not led by one of the politicians indicted by Spain's judiciary.
Catalan secessionist parties failed on Thursday for a third time to elect a regional president, leaving them with a deadline of two months to pick someone or hold a new election.
He was due to appear in court Friday along with several other leading separatists. If they can not agree to a government in two months, another regional election will be held.