He first appears in episode 64 but his fight with Natsu doesn't really start till episode 65 then it's finished in episode 67.
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Synopsis for episode 2: In Magnolia, Natsu and Happy bring Lucy to the Fairy Tail guildhall in Magnolia. Joining Fairy Tail, Lucy overhears a conversation between the guild master Makarov Dreyar and Romeo Conbolt to search for his father Macao. Unable to wait for Macao, Natsu and Happy decide to go find the wizard. Lucy travels with Natsu and Happy to Mt. Hakobe and search for Macao. They encounter a monster called a Vulcan and Lucy is captured. Natsu arrives and fights him, but is thrown out of a hole. Lucy summons Taurus to fight the Vulcan, but Natsu goes back into the mountain and inadvertently knocks out Taurus. Natsu defeats the Vulcan and find out that it took control of Macao's body. After saving Macao, the four return to Magnolia where Romeo reunites with his father.
it starts at episode 81 but im not really sure
episode 113
Their first fight is over episodes 435 and 436, their second fight is 449 and 450.
that episode does not exist