The deal could boost refining capacity in the country by 180,000 barrels a day, with two of the refineries due for completion this year.
As a result, it is forced to import much of its fuel at great cost.
The memorandum of understanding with Vulcan marked "the beginning of changing our old paradigm of exporting just raw materials and exporting jobs to Western countries," said Nigeria's Trade and Investment Minister Olusegun Aganga.
NNPC, after a probe into the industry found $6.8bn had been lost due to fraud in the past two years.
The fuel sector probe was set up in the wake of angry protests in January after the government tried to remove a fuel subsidy.
The government says subsidising fuel cost the country $8bn in 2011.
But the probe found that the government had been paying subsidies on more fuel than the country consumed.