The courts meanwhile placed Catalan police officials and pro-independence civil leaders under investigation for alleged "sedition" as Spain sank deeper into its worst political crisis in decades.
King Felipe VI branded the independence drive illegal and undemocratic, throwing his weight behind the national government.
But Catalan leaders dug in, buoyed by anger at a violent police crackdown against voters during Sunday's referendum on independence which had been banned by Madrid and the courts.
He was scheduled to give a further televised address at 1900 GMT today.
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The Catalan government's spokesman Jordi Turull said that regional authorities had "nearly finished counting the votes."
The result will be submitted to the regional parliament which will have two days "to proclaim the independence of Catalonia," he said in a television interview.
The move would intensify the standoff with the central government, which along with the national courts has branded the referendum illegal.
Prime Minister Mariano Rajoy has yet to respond publicly to Sunday's vote, but the king's intervention could clear the way for him to act.
"It is the responsibility of the legitimate state powers to ensure constitutional order," Felipe said.
Hundreds of thousands of Catalans rallied in fury yesterday during a general strike over violence by Spanish riot police against voters taking part in the referendum on Sunday.
Felipe's dramatic intervention late Tuesday was a gauge of tension in Spain.
Catalan leaders "with their irresponsible conduct could put at risk the economic and social stability of Catalonia and all of Spain," he said.
But after Sunday's violence, his address risked further fanning resentment in Catalonia.
"It was awful. It was a mistake whichever any way you look at it," Turull said of the king's speech.
"Instead of calming things, what it did was throw fuel on the fire."
Adding to tensions, a judge on Wednesday placed Catalonia's regional police chief Josep Luis Trapero and three other suspects under investigation for an alleged "crime of sedition."
The force has been accused of failing to rein in pro- independence protesters during disturbances in Barcelona last month.
Spain's key IBEX 35 stock index fell by 2.3 per cent tOday on the ongoing turbulence, with some big Catalan banks down more than six percent.
Catalan claims for independence date back centuries but have surged during recent years of economic crisis.
Puigdemont's regional government claimed that 2.26 million people took part in the poll, or just over 42 percent of the electorate, but the vote was held without regular electoral lists or observers.