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There is evidence that we made beer before bread. That's the kind of scale we're talking here.
My understanding of the current theory.
Grains were eaten as a porridge.
People started to realise if you let some watery porridge sit open for a few days, something good happens.
People experimented...beer was created.
People then found adding beer to ground grains to be baked caused it to rise.
People experimented...bread was created.