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Citgo Aruba, as the venture is known, will allow Venezuela to process extra-heavy crude from the Orinoco belt, Citgo and PDVSA said in a joint statement.
In June, PDVSA said it planned to invest US$450-650mn to upgrade the refinery in San Nicolas, which is expected to resume production within "18-24 months."
Owned by the Aruba government, the facility has been idle since Valero Energy Corp halted operations in 2012 citing inadequate margins.
PDVSA said it would also produce naphtha at the refinery to dilute heavy crude.