The blast at the facility in the northwestern town of Buritica generated large amounts of toxic gas, local disaster relief official Cesar Hernandez told reporters.
Hernandez said search and rescue crews recovered the bodies of four miners, who died after inhaling the poisonous fumes.
Of the injured, 65 were treated at the scene while 16 were taken to area hospitals.
Authorities have launched an investigation into the incident, which comes several weeks after the mine received an eviction order due to safety lapses and unstable ground conditions.
Fifty-six per cent of Colombia's mines have no operating license.
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