They first found and used oil in babylon about 4000 years ago (!!!) and used it as a building material and some people used it for lighting. It’s hard to say when they worked out quite how much energy you could produce, because lighting it is using it’s energy for useful purposes. But it won’t have been used to power generators, like it is today, until electricity came along in the late 19th century.
Natural gas (a fossil fuel) is old and was first used around 500 B.C. by the Chinese. They found places where natural gas was seeping to surface and used bamboo shoots (pretty resourceful) to transport the gas and used this gas to boil seawater to make it drinkable.
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