Elements have been known since antiquity, especially those that can be found pure in nature.  In most likelihood gold, silver, copper, iron, lead, tin, mercury, sulfur, and carbon were elements recognized before recorded history.  Gold, silver, copper, sulfur and carbon are found pure in nature and referred to as native minerals.  Tin and mercury were probably discovered when an ore containing these elements was exposed to fire to produce a pure element.   These substances were very important to early humans as they used them to create tools for everyday life and to protect themselves (weapons and armor).  A kingdom that possessed these elements was indeed rich. 

All other elements were discovered by experimentation.  Extracting an element or creating an element from other compounds was not an easy task.  Prior to the 17^th century alchemists tried to design experiments to create gold from existing minerals.  One of the first elements to be discovered while looking for gold was phosphorous.  Hennig Brandt (c.1630-1710) was a German who used 50-60 buckets of urine to extract (after a lengthy and stinky process) a small amount of liquid that would solidify and produce a pale-green glow.  Human urine contains PO₄ (phosphate), and he found a process to extract the P (phosphorous),   He was, like most alchemist of this time, looking for gold, but the glowing liquid did give him some recognition.