It happened before written record so we don’t know exactly, but it probably happened by accident.
People discovered copper and tin working long before they developed iron working, and this is almost certainly due to the much lower melting point of those metals and their ores.
You can accidentally process copper ore by using it to build a fire pit, and then noticing later than some of your rocks have melted into a metallic puddle.
Then people learn that just copper or just tin are flimsy, but when you melt them together you get a metal that’s suitable for armor and weapons and tools – bronze.
Iron is more difficult to produce, and very early sources came from iron meteorites that were already relatively pure. Making iron was much less of an accident, people were already familiar with bronzeworking and meteoric iron, and instead needed to develop furnaces capable of sustaining extremely high temperatures to melt down iron and its ores.
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