The flames which were captured on, amateur mobile phone footage, rose high above the refinery buildings and also caused damage to nearby homes.
Vice President Elias Jaua told local reporters, that the majority of the dead were members of the National Guard.
He said, "four people are in hospital right now, two were transferred to Zulia state and 50 people, thank God, were sent home after treatment because their injuries were not serious".
The deadly blast, caused by a gas leak, followed several minor accidents and unplanned stoppages that have afflicted state oil company PDVSA over the last decade, prompting critics to accuse President Hugo Chavez's government of mismanagement.
