Could Superman defeat the Hulk
No, Superman could defeat Tony Stark in the Hulkbuster armor. The Hulkbuster armor proved unable to actually defeat the Hulk, and many of its primary systems were based on particular aspects of the Hulk that don't apply to Superman (for example, the nanotechnology meant to suppress Hulk's ability to remain transformed).
However, if Stark had armor made of Kryptonite, had Kryptonite weapons in the armor, or used artificial red sunlight as a weapon, it might defeat Superman. And/or if Superman's personal physical condition were below optimal levels for whatever reason, that would also affect the outcome. But at full strength and with Stark having only the regular Hulkbuster armor, I don't believe Stark would win.
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